Reaction of perfluoroolefins with Bis (Silyl) ethers to produce fluorinated compounds

ABSTRACT

A reaction of perfluoroolefins with bis(silyl) ethers to produce novel partially fluorinated and perfluorinated copolymers and macrocyclic compounds is disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 07/645,030, filed Jan. 23,1991, U.S. Pat. No. 5,243,025, which is a continuation-in-part of U.S.application Ser. No. 07/243,396, filed Sep. 12, 1988 abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Polymers with high levels of fluorine have novel properties includingchemical and thermal resistance.

This invention provides a novel route to fluorinated polyethers byreacting perfluoroolefins with bis(silyl) ethers in the presence of acatalyst to produce partially fluorinated and perfluorinated copolymersand macrocyclic compounds, partially fluorinated bis(vinyl) ethers andperfluorinated bis(alkyl) ethers. The compositions of this invention areuseful in vapor phase soldering, as lubricants and as heat stable oilsand greases.

2. Technical Background

Hans R. Kricheldorf and Gerhard Bier, Journal of Polymer Science,Polymer Chemistry Edition, Vol. 21, 2283-2289 (1983) disclose thecondensation polymerizations of bis(4-fluorphenyl) sulfone with the bistrimethylsilyl derivatives of bisphenol-A, 4,4'-dihydroxydiphenyl,4,4'-dihydroxydiphenyl sulfone, 1,5-dihydroxynaphthalene,3-hydroxybenzoic acid, and 4-hydroxybenzoic acid. Thesepolycondensations were only successful when potassium or cesium fluoridewas used as a catalyst.

Hans R. Kricheldorf and Gerhard Bier, Polymer, Vol. 25, 1151 (1984)disclose the bulk condensations of 4,4'-difluorobenzophenone and varioussilylated bisphenols at 220° C.-320° C. with cesium fluoride as acatalyst.

U.S. Pat. No. 4,474,932 discloses and claims a process for thepreparation of aromatic ethers or polyethers by reacting aromaticfluorine compounds, in which one or more fluorine substituents areattached to an aromatic nucleus, with trialkylsilyl derivatives ofphenols, in which one or more trialkylsilyl groups are attached to theresidue of a mono or polyphenol, or by reacting trialkylsilylderivatives of fluorophenols with elimination of trialkylfluorosilane.

D. G. Saunders, Systhesis; No. 5, Communications, 377 (1988) dislosesthe reaction of aryl silyl ethers with alkyl halide, or activated arylhalide, and tetrabutylammonium fluoride, to give alkyl aryl ethers ordiaryl ethers, respectively. Alkyl silyl ethers under the same orrelated reaction conditions give mainly the corresponding alcohol, andonly very low yields of the ether.

U.S. Pat. No. 3,549,606 claims fluoroalkyl ether polymers of alicyclicfluoroolefins comprised of repeating units of the structure: ##STR1##wherein n=1-7, y is at least 2 and m is a number from 1-12.

U.S. Pat. No. 3,497,563 claims ethers of the formula: ##STR2## wherein:

E is selected from the group consisting of hydrogen, fluorine and --CH₂OH and may be --CH₂ OH only when T, G and Z are halogen;

G is selected from the group consisting of fluorine and --OCH₂ (CF₂)_(m)D and is fluorine when T is --CH₂ (CF₂)_(n) D;

T is selected from the group consisting of bromine, chlorine and --OCH₂(CF₂)_(m) D and is a halogen when G and Z are --OCH₂ (CF₂)_(m) D;

Z is selected from the group consisting of fluorine and --OCH₂ (CF₂)_(m)D and is fluorine when T is --OCH₂ (CF₂)_(m) D;

D is selected from the group consisting of hydrogen and fluorine; and

n is a number from 1-7 and each m expression is a number from 1 to 12.That invention also claims a method for producing an unsaturatedfluorine containing alicyclic ether by reacting cyclic olefin of theformula: ##STR3## where L is selected from the group consisting offluorine, bromine and chlorine with a fluoroalkanol, in the presence ofan alkali metal hydroxide.

SUMMARY OF THE INVENTION

The present invention provides a polymer consisting essentially of therepeat unit:

    --[(CR.sub.f.sup.1)C═C(R.sub.f.sup.2)ORO]--            (A)

wherein:

R is a diradical of the formula --C_(x) H_(2x-y) F_(y) --, where x is aninteger from 2 to 20, y is 0 or an integer from 1 to 2x for a givenvalue of x, but with the additional proviso that the carbon atomscontaining the free valence of the diradical not be attached to fluorineatoms, and when x is a integer from 4 to 20 some of the carbon atoms maybe internally interrupted with oxygen atoms forming either structuresand with the proviso that the oxygen atoms be separated by two or morecarbon atoms; --C₆ H₄₋₁ F_(a) --, wherein a is 0, 1, 2, 3, and 4; --C₁₀H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6, with theproviso that the radical bonds are not on adjacent carbon atoms; --C₁₂H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8, with theproviso that the radical bonds are not on adjacent carbon atoms; and--CH_(4-d) F_(d) -R¹ --C₆ H_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --C_(x) H_(2x-f) F_(f)--, wherein f is 0 or an integer from 1 to 2x;

R_(f) ¹ and R_(f) ² are independently --C_(z) CF_(2z+1), wherein z is aninteger from 1 to 10; or R_(f) ¹ and R_(f) ² taken together where R_(f)¹ and R_(f) ² in the cis configuration are --(CF₂)_(m) --, wherein m is2, 3 or 4, provided that when R_(f) ¹ and R_(f) ² are as defined, then Rshall not be --CH₂ (CF)_(s) CH₂ -- where s is an integer from 1 to 12,C₆ F₅ --, C₁₀ F₇ -- or C₁₂ F₉ --.

The invention additionally provides polymers consisting essentially ofthe repeat unit:

    --[C(═CFR.sub.f.sup.1)OR.sup.8 O]--                    (B)

wherein R_(f) ¹ is as defined above; R⁸ is R as defined above with theproviso that one of the carbon atoms adjacent to the carbon atomscontaining the free valence of the diradical be attached to at least twofluorine atoms.

The invention additionally provides a macrocyclic compound of thestructures: ##STR4## wherein R_(f) ¹, R_(f) ², R and R⁸ are as definedabove and w is 1, 2, 3 or 4.

The invention additionally provides bis(vinyl) ethers of the structures:

    R.sub.f.sup.1 (F)C═C(R.sub.f.sup.2)OROC(R.sub.f.sup.2)═C(F)R.sub.f.sup.1, (D)

    R.sub.f.sup.1 (F)C═C(F)OR.sup.8 OC(F)═C(F)R.sub.f.sup.1, and (E)

    R.sub.f.sup.1 R.sub.f.sup.2 C═C(R.sub.f.sup.6)OR.sup.8 OC(R.sub.f.sup.6)═CR.sub.f.sup.2 R.sub.f.sup.1        (E')

wherein R_(f) ¹, R_(f) ², R and R⁶ are defined above and R_(f) ⁶ is thesame as R_(f) ¹.

The invention additionally provides a polymer consisting essentially ofthe repeat unit:

    --[(R.sub.f.sup.4)(F)CC(F)(R.sub.f.sup.5)OR.sub.f.sup.3 O]--(J)

wherein:

R_(f) ³ is a diradical selected from --C_(x) F_(2x) --, where x is aninteger from2 to 20; when x is an integer from 4 to 20, some of thecarbon atoms may be internally interrupted with oxygen atoms formingether structures, with the proviso that the oxygen atoms be separated bytwo or more carbon atoms; R_(f) ⁴ and R_(f) ⁵ are independently selectedfrom C_(z) F_(2z+1), z is an integer from 1 to 10 or R_(f) ⁴ and R_(f) ⁵taken together are --(CF₂)--_(m), and m is 2, 3 or 4, and wherein noolefinic unsaturation is present in the polymer.

The invention additionally provides a polymer consisting essentially ofthe repeat unit:

    --[CF(CF.sub.2 R.sub.f.sup.4)OR.sub.f.sup.3 O]--           (K)

wherein R_(f) ³ and R_(f) ⁴ are as defined above.

The invention additionally provides acyclic compound of the structure:##STR5## wherein R_(f) ³, R_(f) ⁴, R_(f) ⁵, and w are as defined above.

The invention additionally provides a bis(perfluoroalkyl)ether of thestructure:

    R.sub.f.sup.4 CF.sub.2 CF(R.sub.f.sup.5)OR.sub.f.sup.3 OCF(R.sub.f.sup.5)CF.sub.2 R.sub.f.sup.4,                 (M)

    R.sub.f.sup.4 CF.sub.2 CF.sub.2 OR.sub.f.sup.3 OCF.sub.2 CF.sub.2 R.sub.f.sup.4, and                                        (N)

    R.sub.f.sup.4 R.sub.f.sup.5 CFCF(R.sub.f.sup.6)OR.sub.f.sup.3 OCF(R.sub.f.sup.6)CFR.sub.f.sup.4 R.sub.f.sup.5           (N')

wherein R_(f) ³,R_(f) ⁴,R_(f) ⁵, and R_(f) ⁶ are as defined above.

In addition, the invention provides processes for the preparation of theabove compositions, A, B, C, C', D, E and E' by a polycondensationreaction of silyl ethers and perfluoroolefins, or, in some cases, with abis(vinyl) ether prepolymer in place of the perfluoroolefin, at selecteddilutions, in the presence of a suitable catalyst which may be a sourceof fluoride ion, such as, but not limited to CsF,tris(dialkylamino)sulfonium difluorotrimethylsilicate,tetrabutylammonium fluoride, tris(dialkylamino)sulfonium bifluorides.The reaction will also proceed with other catalysts which are notsources of fluoride ion including M⁺ ZCO₂ ⁻, M⁺ OC₆ H₄ NO₂ ⁻ and M⁺ ZSO₂⁻ where z is a linear or branched alkyl group containing from 1 to 10carbon atoms or phenyl group and M⁺ is any cation preferably (Z'₂ N)₃S⁺. Z' is a linear or branched alkyl group containing from 1 to 10carbon atoms.

The temperature of the reactions to prepare the above compositions canrange from about -50° C. to 120° C. The processes can proceed in thepresence of a solvent that does not react with reagents or products orin the absence of any solvent.

Compounds J, K, L, L', M, N, and N' are prepared by reacting elementalfluorine with compositions A-E'.

DETAILS OF THE INVENTION

The novel reaction of bis(silyl) ethers with perfluorinated olefins hasbeen used to synthesize a series of partially fluorinated polymers,bis(vinyl) ethers and macrocyclic structures. These partiallyfluorinated compounds can in turn react with elemental fluorine toproduce a series of novel perfluoro polymers bisperfluoroalkyl ethers,and perfluoromacrocyclic structures.

The partially fluorinated products have utility as heat stable liquidsand greases. The perfluorinated structures have utility as lubricantsand heat stable fluids.

By a polymer herein is meant a compound with two or more repeat unitsthat is not cyclic.

In the polymer (A), the groups --C₆ H_(4-a) F_(a) --, --C₆ H_(4-d) F_(d)-- and --C₆ H_(4-e) F₃ -- means a (fluorinated) phenylene group, thegroup --C₁₀ H_(6-b) F_(b) -- means a (fluorinated) naphthylylene group,and the group --C₁₂ H_(8-c) F_(c) -- means a biphenylene group. With theproviso that the radical bonds are not on adjacent (ring) carbon atoms,the phenylene group could be, for example, meta- or para-phenylene.

The invention provides a process for the preparation of (A) by apolycondensation reaction of R² R³ R⁴ SiOROSiR⁵ R⁶ R⁷ (F) and R_(f) ¹(F)C═C(F)R_(f) ² (G) in the presence of a catalyst, wherein R², R³, R⁴,R⁵, R⁶, and R⁷ are independently CH₃ -- or C₂ H₅ -- or one of R², R³,R⁴, R⁵, R⁶, and R⁷ may be C₆ H₅ -- with the remainder of the groupsbeing independently CH₅ or C₂ H₅ --, and R, R_(f) ¹ and R_(f) ² are asdefined above.

In the above process, a bis(vinyl) either [which can be considered aprepolymer] of structure R_(f) ¹ (F)C═C(R_(f) ²)ORO(R_(f) ²)C═C(F)R_(f)¹ can be used in place of R_(f) ¹ (F)C═C(F)R_(f) ² in the polymerizationprocess. The use of a prepolymer offers the advantage of more precisemeasurement of starting materials and higher degree of control overolefin reactivity.

The polymerization reaction is normally done in a solvent such a glymeor tetrahydrofuran. However, any organic or inorganic compound may beused as solvent so long as the compound does not interact with thestarting materials or interfere with the polymerization reaction underreaction conditions. The reaction can be done in the absence of solventif so desired.

The molar ratio of perfluoroolefin to bis(silyl) ether can range from0.9 to 2.5. The molar ratio of bis(vinyl) ether to bis (silyl) ether canrange from 0.9 to 1.5. The molar ratio of bis(silyl) ether to catalystcan range from 4 to 10,000. The concentration of bis(silyl) ether insolution is greater than or equal to 0.01 M. The temperature of thepolymerization reaction can range from -50° C. to 120° C. The polymercan be recovered by removing solvent and volatile by-products by heatingunder vacuum.

Preferred bis(silyl) ethers are those in which R², R³, R⁴, R⁵, R⁶, andR⁷ are --CH₃ and R is a --CH₂ (CF₂)₃ CH₂ --, --CH₂ (CF₂)₂ O[CF(CF₃)CF₂O]_(h) CF(CF₃)CH₂ -- where h is 0, 1, 2, 3 or 4, --(CH₂)₄ --, --CH₂(CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ --, or -p-C₆ H₄ C(CF₃)₂ C₆ H₄ -p-.

Preferred perfluoroolefins are those in which R_(f) ¹ and R_(f) ² are--CF₃ and where R_(f) ¹ and R_(f) ² taken together are --(CF₂)₂ --.

The invention additionally provides a process for the preparation of (B)by a polycondensation reaction of R² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ (H) andR_(f) ¹ (F)C═CF₂ (I) in the presence of a catalyst, preferably CsF.R_(f) ¹, R_(f) ², R_(f) ³, R_(f) ⁴, R_(f) ⁵, R_(f) ⁶, R_(f) ⁷, and R_(f)⁸ are as defined above.

Bis(vinyl) ethers [prepolymer] of structure R_(f) ¹ (F)C═C(F)OR⁸O(F)C═C(F)R_(f) ¹ can be used in place of R_(f) ¹ (F)C═CF₂ in thepolymerization process.

The polymerization reaction conditions and solvents are as described for("A") above. Preferred conditions for the polymerization reaction toyield B are when the temperature range is -20° C. to +10° C., thecatalyst is CsF and the solvent is glyme or THF.

Preferred bis(silyl) ethers are those in which R², R³, R⁴, R⁵, R⁶, andR⁷ are --CH₃ and R⁸ is --CH₂ (CF₂)₃ CH₂ --, and --CH₂ (CF₂)₂O[CF(CF₃)CF₂ O]_(h) CF(CF₃)CH₂ -- with h 0, 1, 2, 3 or 4.

Preferred perfluoroolefins are those in which R_(f) ¹ is --CF₃, or --C₂F₅.

The invention additionally provides macrocyclic compounds of thefollowing structures: ##STR6## where R_(f) ¹, R_(f) ², R and R⁸ are asdefined above and w is 1 to 4.

The invention additionally provides a process for the preparation of (C)by a condensation reaction of R² R³ R⁴ SiOROSiR⁵ R⁶ R⁷ (F) and R_(f) ¹(F)C═C(F)R_(f) ² (G) in dilute solutions in the presence of a catalyst.

The preferred catalysts are CsF and tris(dialkylamino)sulfoniumdifluorotrimethyl silicate. R_(f) ¹, R_(f) ², R, R², R³, R⁴, R⁵, R⁶, andR⁷ are as defined above.

A bis(vinyl) ether of structure R_(f) ¹ (F)C═C(R_(f) ²)ORO(R_(f)²)C═C(F)R_(f) ¹ can be used in place of R_(f) ¹ (F)C═C(F)R_(f) ² in thecyclization process and is preferred for highest yields. However, whenbis(vinyl) ether is used only the macrocyclic structures with w=2 or 4can be synthesized.

The cyclization reaction is normally done in a solvent such as glyme ortetrahydrofuran. However, any organic or inorganic compound may be usedas solvent so long as the compound does not interact with the startingmaterials or interfere with the cyclization reaction under reactionconditions. The molar ratios are as above except that the concentrationof bis(silyl) ether in solution can range from 0.0001 M to 0.1 M.

The temperature of the cyclization reaction can range from -50° C. to120° C.

The cyclic compound can be recovered by removing solvent and volatileby-products by heating under vacuum. The cyclic compound can be purifiedby conventional methods such as vacuum distillation, chromatographyand/or crystallization.

Preferred bis(silyl) ethers are those in which R², R³, R⁴, R⁵, R⁶, andR⁷ are --CH₃ and R is --CH₂ (CF₂)₃ CH₂ --, --CH₂ (CF₂)₂ O[CF(CF₃)CF₂O]_(h) CF(CF₃)CH₂ -- where h is 0, 1, 2 3 or 4, --(CH₂)₄ --, and --CH₂(CH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ --.

Preferred perfluoroolefins are those in which R_(f) ¹ and R_(f) ² takentogether (R_(f) ¹ and R_(f) ² in cis configuration) are --(CF₂)₂ --.

The invention additionally provides a process for the preparation of(C') by a condensation reaction of R² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ (H) andR_(f) ¹ (F)C═CF₂ (I) in dilute solution in the presence of a catalystsuch as CsF. R_(f) ¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are as definedabove.

Bis(vinyl) ethers of structure R_(f) ¹ (F)C═C(F)OR⁸ O(F)C═C(F)R_(f) ¹can be used in place of R_(f) ¹ (F)C═CF₂ in the cyclization process andis preferred for highest yields. However, when bis(vinyl) ethers areused only macrocyclic compounds with w=2 or 4 can be synthesized.

The cyclization reaction is normally done in a solvent such as glyme ortetrahydrofuran in dilute solutions, as described for (C) above.

Preferred bis(silyl) ethers are those in which R², R³, R⁴, R⁵, R⁶, andR⁷ are --CH₃ and R⁸ is --CH₂ (CF₂)₃ CH₂ --, and --CH₂ (CF₂)₂O[CF(CF₃)CF₂ O]_(h) CF(CF₃)CH₂ -- where h is 0, 1, 2, 3 or 4.

Preferred perfluoroolefins are those in which R_(f) ¹ is --CF₃ or --C₂F₅.

The invention additionally provides a process for the preparation of (D)by a condensation reaction of R² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ (F) and R_(f) ¹(F)C═C(F)R_(f) ² (G) in the presence of a catalyst. The preferredcatalysts are CsF and tris(dialkylaminosulfonium difluorotrimethylsilicate. R_(f) ¹, R_(f) ², R, R², R³, R⁴, R⁵, R⁶, and R⁷ are as definedabove.

The condensation reaction is normally done in a solvent such as glyme ortetrahydrofuran. However, any organic or inorganic compound may be usedas solvent so long as the compound does not interact with the startingmaterials of interfere with the condensation reaction under reactionconditions.

The molar ratio of bis(silyl) ether to catalyst can range from 4 to10,000. The molar ratio of perfluoroolefin to bis(silyl) ether can rangefrom 2.2 to 12. The concentration of bis(silyl) ether in solution isgreater than or equal to 0.01 M. The temperature of the condensationreaction can range from -50° C. to 120° C. The prepolymer can berecovered by removing solvent and volatile by-products by heating undervacuum. The prepolymer can be purified by vacuum distillation.

Preferred bis(silyl) ethers are those in which R², R³, R⁴, R⁵, R⁶, andR⁷ are --CH₃ and R is --CH(CH₃)CH₂ --, --(CH₂)₃ --, --(CH₂)₄ --,--(CH₂)₅ --, --(CH₂) (CF₂)₃ CH₂ --, --CH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂--, --CH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]_(h) CF(CF₃)CH₂ -- where h is 0, 1, 2, 3or 4, and --(p-C₆ H₄)C(CF₃)₂ (p-C₆ H₄)--. Preferred perfluoroolefins arethose in which R_(f) ¹ and R_(f) ² taken together are --(CF₂)₂ --,--(CF₂)₃ --; R_(f) ¹ and R_(f) ² are --CF₃.

The invention additionally provides a process for the preparation of (E)by a condensation reaction of R² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ (H) with excessR_(f) ¹ (F)C═CF₂ (I) in the presence of a catalyst such as CsF, whereinR_(f) ¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are as defined above.

The reaction is normally done in a solvent and with molar ratios asdescribed for (D).

Preferred bis(silyl) ethers are those in which R², R³, R⁴, R⁵, R⁶, andR⁷ are --CH₃ and R⁸ is --CH₂ (CF₂)₃ CH₂ --, and --CH₂ (CF₂)₂O[CF(CF₃)CF₂ O]_(h) CF(CF₃)CH₂ -- where h is 0, 1, 2, 3, or 4.

Preferred perfluoroolefins are those in which R_(f) ¹ is --CF₃, --C₂ F₅.

The invention additionally provides a process for the preparation of(E') by a condensation reaction of R² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ (F) andR_(f) ¹ R_(f) ² C═C(F)R_(f) ⁶ (Q) in the presence of a catalyst. Thepreferred catalysts are CsF and tris(dialkylamino)sulfoniumdifluorotrimethyl silicate. R_(f) ¹, R_(f) ², R, R², R³, R⁴, R⁵, R⁶, R⁷and R⁸ are as defined above.

The condensation reaction is normally performed in a solvent under theconditions and with molar concentrations as for (E) above.

Preferred bis-silyl ethers are those in which R², R³, R⁴, R⁵, R⁶, and R⁷are --CH₃ and R is --CH₂ (CF₂)₃ CH₂ --, --CH₂ (CF₂)₂ OCF(CF₃)CF₂OCF(CF₃)CH₂ --, --CH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]_(h) CF(CF₃)CH₂ -- where his 0, 1, 2, 3 or 4, and -(p-C₆ H₄)C(CF₃)₂ (p-C₆ H₄)--.

Preferred perfluoroolefins are those in which R_(f) ¹ and R_(f) ² are--CF₃ -- and R_(f) ⁶ is --CF₃ CF₂ --.

These bis(vinyl) ethers can also be used as intermediates for furtherpolymerization with bis(silyl) ethers but the structure of the polymeris unknown.

(J) is prepared by reacting (A) with elemental fluorine when R, ascontained in (A), is --C_(x) H_(2x-y) F_(y) --, as defined above. Thefluorination procedure includes dissolving the intermediate in an inertsolvent, purging the system with an inert gas to expel dissolved oxygen,cooling or heating the mixture to a proper reaction temperature andpassing the fluorine gas in an oxygen-free inert gas stream through thesolution. The solution is irradiated by means of an ultraviolet lamp.All fluorination processes herein result in the replacement of allhydrogen in the polymer with fluorine, and fluorination of all olefinicbonds to fluorinated saturated alkyl groups.

(K) is prepared by reacting (B) with elemental fluorine, when R⁸, ascontained in (B), is --C_(x) H_(2x-y) F_(y) --, as defined above. Thefluorination procedure is performed as described for (J) above.

(L) is prepared by reacting (C) with elemental fluorine, when R, ascontained in (C), is --C_(x) H_(2x-y) F_(y) --, as defined above. Thefluorination procedure is performed as described for (J) above.

(L') is prepared by reacting (C') with elemental fluorine, when R⁸, ascontained in (C'), is --C_(x) H_(2x-y) F_(y) --, as defined above. Thefluorination procedure is performed as described for (J) above.

(M) is prepared by reacting (D) with elemental fluorine when R, ascontained in (D), is --C_(x) H_(2x-y) F_(y) --, as defined above.

(N) is prepared by reacting (E) with elemental fluorine, when R⁸, ascontained in (E), is --C_(x) H_(2x-y) F_(y) --, as described above.

(N') is prepared by reacting (E') with elemental fluorine, when R, ascontained in (E'), is --C_(x) H_(2x-y) F_(y) --, as described above. Thefluorination procedures for M, N and N' are performed as described for(J) above.

The macrocyclic structures C, and C' can interact with F⁻ to formmacrocyclic anions. The F⁻ is bound to the cyclic structure by multipleC-H-anion interactions. The macrocyclic anions have been shown to becatalysts for the condensation reactions described in this applicationand for group transfer polymerization of methyl methacrylate.

EXAMPLES EXPERIMENTAL

Fluorine chemical shifts are reported in ppm from CFCl₃. Spectra wererecorded on a Nicolet NT200 spectrometer at 188.2 MHz. ¹ H NMR spectrawere recorded on a GE QE-300 spectrometer, and chemical shifts arereported relative to tetramethylsilane at 0 ppm. Infrared spectra wererecorded on a Perkin-Elmer 983G infrared spectrometer.

Mass spectral data were obtained using VG 7070-HS (with Varian Vista6000 GC), VG 70-SE (with HP 5790 GC), VG ZAB-2F (high resolution), or VGZAB-E (low resolution instruments.

Gas chromatography was done using a Hewlett Packard 5890 instrument with25 m×0.2 m HPl crosslined methyl silicone capillary column, operating at60-250° C. (method 1).

Molecular weights (M_(w) and M_(n)) were determined by size exclusionchromatography using polystyrene standards.

Solvents with minimum water concentrations were preferred for thereactions described herein. Tetrahydrofuran (THF), dimethoxyethane(glyme), and ether were distilled from sodium/benzophenone and storedunder nitrogen. Other solvents were distilled and stored over activatedmolecular sieves.

Unless indicated otherwise, all reactants are either known compounds orcan be prepared by known methods. All reactions were carried out in anatmosphere of dry nitrogen, and manipulations of hygroscopic or watersensitive catalysts were done in a Vacuum Atmospheres drybox.Low-boiling fluoroolefins were transferred to gas traps and measured byvolume unless described otherwise.

Experiment 1

Preparation of (CH₃)₃ SiO(CH₂)₂ OSi(CH₃)₃

Hexamethyldisilazane (HMDS) (104 g, 0.64 mol) was added to distilledethylene glycol (40 g, 0.64 mol) and the mixture was heated at 80° C.for 18 h. Distillation gave 103 g of colorless oil, bp 88° C./50 mm.Although the first portion to be collected was contaminated withlower-boiling materials, the latter portion was of high purity (99% byGC; methyl silicone gum, 80-225° C.). ¹ H NMR (CDCl₃): 3.60 (s, 4 H),0.13 (s, 18 H) consistent with the assigned structure.

Experiment 2

Preparation of (CH₃)₃ SiO(CH₃)₃ OSi(CH₃)₃

1,3-Propanediol (47.8 g, 0.63 mol) was placed in a 500 mL 3-necked RBflask and treated with 0.3 mL trimethylsilyl chloride. A portion of HMDS(ca. 25 mL) was added, and an exothermic reaction took place as themixture became homogeneous. The remainder of the HMDS (121 mL, 0.69 moltotal) was added at a controlled rate (ca. 3-5 mL/min), maintaining thereaction temperature at ca. 60° C. Heating was continued at 100° C. (3h), and 150° C. (1.5 h). Distillation provided 130.6 g of colorless oil,bp 80-81° C./15 mm. GC analysis (method 1) showed ca. 99% purity.

Experiment 3

Preparation of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃

1,4-Butanediol (54 g, 0.60 mol) was placed in a 500 mL 3-necked RB flaskand treated with 0.3 mL trimethylsilyl chloride. A portion of HMDS (ca.20 mL) was added, and an exothermic reaction took place as the mixturebecame homogeneous. The remainder of the HMDS (120 mL, 0.66 mol total)was added at a controlled rate (ca. 3-5 mL/min), maintaining thereaction temperature at ca. 50° C. Heating was continued at 100° C. (3h), and 150° C. (1.5 h). GC analysis (method 1) revealed excess HMDS andone product. Distillation provided 127.8 g of colorless oil, bp 97-99°C./15 mm. ¹ H NMR (CDCl₃): 3.75-3.50 (m, 4 H), 1.75-1.50 (m, 4 H), 0.16(s, 18 H).

Experiment 4

Preparation of (CH₃)₃ SiO(CH₂)₅ OSi(CH₃)₃

1,5-Pentanediol (65 g, 0.62 mol) was placed in a 500 mL 3-necked RBflask and treated with 0.4 mL trimethylsilyl chloride. A portion of HMDS(ca. 20 mL) was added, and an exothermic reaction took place as themixture became homogeneous. The remainder of the HMDS (130 mL, 0.71 moltotal) was added at a controlled rate (ca. 3-5 mL/min), maintaining thereaction temperature at ca. 50° C. Heating was continued at 100° C. (1h), and 150° C. (2.5 h). GC analysis (method 1) revealed excess HMDS andone product. Distillation provided 139 g of colorless oil, bp 47-49°C./0.1 mm. ¹ H NMR (CDCl₃): 3.60 (t, J=7 Hz, 4 H), 1.57 (m, 4 H), 1.40(m, 2 H), 0.12 (s, 18 H), consistent with the assigned structure.

Experiment 5

Preparation of (CH₃)₃ SiOCH(CH₃)CH₂ OSi(CH₃)₃

1,2-Propanediol (58.8 g, 0.77 mol) was placed in a 500 mL 3-necked RBflask and treated with 0.2 mL trimethylsilyl chloride. A small volume ofHMDS (ca. 10 mL) was added, and an exothermic reaction took place as themixture became homogeneous. The remainder of the HMDS (170 mL) was addedat a controlled rate (ca. 3-5 mL/min), maintaining the reactiontemperature at ca. 50-70° C. Heating was continued at 100° C. (1.5 h),120° C. (1.0 h), and 140° C. (2.5 h). GC analysis (method 1) revealedexcess HMDS and one product. Distillation provided 147 g of colorlessoil, bp 70-72° C./10 mm. ¹ H NMR (CDCl₃): 3.83 (m, 1 H), 3.50 and 3.38(AB pattern with additional coupling, 2 H), 1.15 (d, J=7 Hz, 3 H), 0.15(partially resolved singlets, 18 H).

Experiment 6

Preparation of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃

A sample of 2,2,3,3,4,4-hexafluoro-1,5-pentanediol (10.3 g, 48.6 mmol)was treated with trimethylsilyl chloride (0.1 mL) and HMDS (8.4 g, 52mmol). The mixture was heated slowly to 80° C. for 2.0 h and was heatedbriefly (ca. 15 min.) at 125° C. Crude product was transferred from thereactor under vacuum and was redistilled to give 16.1 g of colorless oil(93% yield), bp 40° C./0.1 mm. GC analysis (method 1) showed >99.8%purity. ¹⁹ F NMR (CDCl₃ /fluorotrichloromethane (F11): -122.4 (m, 4 F),-126.4 (s, 2 F). ¹ H NMR (CDCl₃): 4.08 (m, 4 H), 0.20 (s, 18 H).

Experiment 7

Preparation of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃

A) Preparation of CH₃ OOC(CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)COOCH₃

A mixture of sodium fluoride (12 g) and methanol (200 mL) was cooled to0° C. and treated slowly with the diaduct ester (CH₃ OOC(CF₂)₂OCF(CF₃)CF₂ OCF(CF₃)COF, DAE) prepared from methyl difluoromalonylfluoride and hexafluoropropylene oxide (HEPO) (116 g, 0.24 mol) asdescribed in U.S. Pat. No. 4,138,426. The mixture was warmed to 25° C.and stirred for 3 h. Filtration and removal of solvent gave a residuewhich was distilled to provide 71.8 g bp 96-103° C./14 mm. GC analysis(method 1) showed two diastereomers with purity >99.8%. ¹⁹ F NMR (CDCl₃/F11): -79.25 and -79.75 (low-field portions of AB patterns, J_(AB) =147Hz, 1 F), -85.75 and -86.30 (upfield portions of AB patterns, 1 F),-80.5 (m, 3 F), -82.8 (s, 3 F), -83.5 (m, 2 F), -121.7 (s, 2 F), -132.2(overlapping m's, ester end CF), -145.9 (apparent t, middle CF).

B) Preparation of HOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OH

A solution of CH₃ OOC(CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)COOCH₃ (68.5 g, 137mmol) in methanol (300 mL) at 0° C. was treated in portions with sodiumborohydride (10.3 g, 271 mmol). Temperature was controlled at 10-20° C.After stirring for 16 h, most of the solvent was removed under vacuum.The residue was diluted with ether, washed with water, saturated sodiumchloride, and dried (MgSO₄). Evaporation gave a residue which waskugelrohr distilled to give 56.3 g, bp 65-72° C./ca. 0.1 mm. GC analysis(method 1) showed two diastereomers (58/42) in >99% purity. ¹⁹ F NMR(acetone-d₆ or THF-d₈): -78.2--84.2 (multiplets, including AB patterns-82.7 and -83.7 (J=145), -78.8 and -80.8 (J˜145), and -79.2 and -81.2(J˜145), -125.16 and -125.22 (triplets, J_(HF) =14 Hz, 2 F), -145.16 and-145.28 (triplets, J_(FF) =22 Hz, 1 F). ¹ H NMR (acetone -d₆): -5.31(doubled triplets, ³ J_(HH) =6.6 Hz), Δυ₃₆₀ MHz =2.3 Hz for twodiastereomers, (1 H), 5.12 (t, ³ J_(HH) =6.8 Hz, 1 H), 4.24 (dd, J=6,12.7 Hz, 2 H), 4.04 (t of doublets, J_(HF) =14.5, J_(HH) =6.0 Hz, 2 H).Addition of a trace of HCl caused the disappearance of hydroxyl protonsignals and simplification of the remaining signals to 4.22 (d, J=13)and 4.03 (t, J=14.4 Hz). ¹ H NMR (THF-d₈): 5.32 (t, J=6.7 Hz, 1 H), 5.13and 5.12 (triplets, J=7 Hz, 1 H), 4.11 (dd, J=6, 12.7 Hz, 2 H), 3.93 (tof d, J=14.5, 6.0 Hz).

C) Preparation of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃

HOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OH (28.8 g, 64.9 mmol) was chilledin ice and treated with HMDS (26.5 g, 164 mmol). The mixture was warmedto 25° C. and stirred for 2.5 h. GC analysis (method 1) showed completeconversion to two diastereomeric products (retention time=11.59, 11.64min) in >99.3% purity. ¹⁹ F NMR (THF-d₈): -79.4 and -81.2 (AB pattern,J_(AB) =160 Hz, 2 F), -79.8 (unresolved m, 3 F), -81.9 and -82.0(singlets, Δυ₁₈₈.2 MHz =13 Hz, 3 F), -82.7 and -83.3 (AB pattern, J_(AB)=160 Hz), -124.6 (t, J=14 Hz) and -124.7 (t, J=14 Hz, combined 2 F),-134.6 (m, 1 F, CFCH₂), -145.04 (t, J=22 Hz) and -145.20 (t, J=22 Hz,combined 1 F, internal CF). ¹ H NMR (THF-d₈): 4.20 (t, J=11.8 Hz, 2 H),4.05 (t, J=13.6 Hz) and 4.04 (t, J=13.6 Hz, 2 H), 0.14 and 0.13, Δυ₁₈₈.2MHz =3.2 Hz). Ratio of diastereomers was 50/50 within experimentalerror.

Experiment 8

Preparation of (CH₃)₃ SiOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂OSi(CH₃)₃

A) Preparation of CH₃ OOC(CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)COOCH₃

A mixture of sodium fluoride (12 g) and methanol (200 mL) was cooled to0° C. and treated slowly with the triadduct ester CH₃ OOC(CF₂)₂O[CF(CF₃)CF₂ O]₂ CF(CF₃)COF, (TAE) prepared from methyl difluoromalonylfluoride and HFPO (136 g) as described in U.S. Pat. No. 4,138,426. Themixture was warmed to 25° C. and stirred for 18 h. Filtration andremoval of solvent gave a residue which was distilled to provide 111 g,bp 55-63° C./0.05 mm. GC analysis (method 1) showed four diastereomerswith purity >98%. ¹⁹ F NMR (acetone-d₆): -78 to -79.5 (low-field portionof AB pattern), -79.8 to -82.8 (m), -84.5 (upfield portion of ABpattern), -121.0 (m, 2 F), -131.0 (overlapping m's, ester and CF),-144.9 (m). IR (thin film): 1790 cm⁻¹.

B) Preparation of HOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂ OH

A solution of CH₃ OOC(CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)COOCH₃ (21.5 g, 32.3mmol) in methanol (100 mL) at 0° C. was treated in portions with sodiumborohydride (2.6 g, 68 mmol). Temperature was controlled at 10-20° C.after stirring for 16 h, most of the solvent was removed under vacuum.The residue was diluted with ether, washed with water, saturated sodiumchloride, and dried (MgSO₄). Evaporation gave a residue which waskugelrohr distilled to give 17.6 g, bp 75° C./0.05 mm. GC analysis(method 1) showed a mixture of diastereomers in >97% purity. ¹⁹ F NMR(acetone-d₆): -78.0 to -84.0 (multiplets, 15 F), -125.1 (m, CH₂ CF₂),-134.5 (m, terminal CF), -145.0 (m, internal CF).

C) Preparation of (CH₃)₃ SiOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂OSi(CH₃)₃

HOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂ OH (17.6 g, 28.9 mmol) waschilled in ice and treated with HMDS (11.8 g, 73.3 mmol). The mixturewas warmed to 25° C. and stirred for 1.0 h. GC analysis (method 1)showed complete conversion to diastereomeric products (retention timeca. 12.3 min). Excess HMDS was removed under vacuum at ca. 40° C. toprovide 21 g of colorless oil. Kugelrohr distillation gave a sample withbp 65° C./0.05 mm. ¹⁹ F NMR (CDCl₃): -79.6 to -84.05 (series of m, CF₃and OCF₂), -125.6 (m, OCH₂ CF₂), -135.8 (m, CH₂ CF), -146.0 (m, internalCF), consistent with the assigned structure.

Experiment 9

Preparation of p-(CH₃)₃ SiOPhC(CF₃)₂ PhOSi(CH₃)₃ -p

Bisphenol AF (50 g, 0.15 mol) in 50 mL glyme was treated with HMDS (50g, 0.3 mol). The mixture was heated slowly and then heated at reflux for2.0 h. GC analysis (method 1) showed quantitative conversion to oneproduct. Low-boiling materials were removed under vacuum, and productwas kugelrohr distilled to provide 70 g of colorless oil whichcrystallized (mp 54-56° C.). ¹ H NMR (THF-d₈): 7.25 and 6.85 (ABpattern, J_(AB) =8 Hz, 8 H), 0.27 (s, 18 H).

Example 1

Preparation of CF₃ (F)C═C(F)OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OC(F)═C(F)CF₃

A solution of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃(23.0 g, 39 mmol) in glyme (100 mL) at -60° C. was treated withhexafluoropropene (HFP) (16.8 g, 112 mmol) and cesium fluoride (1.3 g).The mixture was warmed slowly (2.0 h) to 0° C. and stirred at thistemperature for 2.0 h. Excess HFP was removed under vacuum. Theremaining mixture was diluted with ether, washed with ice water andsodium chloride solution, dried, and evaporated to provide 29.1 g ofcrude product. Kugelrohr distillation gave 14.7 g, bp 35-47° C./0.1 mm.Spinning band distillation removed small amounts of lower-boilingmaterials and gave a center cut of title compound (5.4 g), bp 47-48°C./0.05 mm. ¹⁹ F NMR (THF-d₈): -67.7 (m, CF₃), -79 to -83.4 (m, CF₃ andOCF₂), -95.5 and -96.2 (m's, vinyl F at C1 trans to CF₃ groups), -111.5(overlapping doublets of quartets, J₃ =125 Hz, vinyl F on C1 cis toCF₃), -123.8 (m, CF₂ CH₂), -134.5 to 135.5 (m, CFCH₂), -144.5 (m,central CF group), -184.0 (overlapping m, vinyl F on C2 "Z"-ends),-189.92 and -190.22 (overlapping d of quartets, J_(d) =120 Hz, vinyl Fon C2, "E"-ends), ¹ H NMR (THF-d₈): -4.81 (t, J=12.9 Hz), 4.87 (t,J=12.7 Hz), 4.96 (d, J=11.4 Hz), 5.03 (d, J=11.5 Hz).

Example 2

Preparation of CF₃ (F)C═C(F)OCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂OC(F)═C(F)CF₃

A solution of (CH₃)₃ SiOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂ OSi(CH₃)₃(12.0 g, 15.9 mmol) in glyme (65 mL) at -60° C. was treated with HFP(6.8 g, 45.6 mmol) and cesium fluoride (0.5 g). The mixture was warmedslowly to 0° C. and stirred at this temperature for 2.5 h. The mixturewas diluted with ether, washed with ice water and sodium chloridesolution, dried, and evaporated to provide 14.5 g of crude product. GCanalysis (method 1) showed four major isomers (65% of the mixture).Kugelrohr distillation gave 8.64 g, bp 70-87° C. (0.1 mm). Spinning banddistillation gave 5.4 g (bp 55-58° C., 0.05 mm). IR: 1769 cm⁻¹ and1250-1140 cm⁻¹ envelope. ¹⁹ F NMR (THF-d₈): -67.8 (m, CF₃), -78.5 to-83.3 (m, CF₃ and OCF₂), -95.6 (d of quartets, J_(q) =9.6 Hz, J_(d)=19.9 Hz, vinyl F on C1 trans to CF₃), -96.4 (d of quartets, J_(d) =9.6Hz, J_(d) =19.9 Hz, vinyl F on C3 trans to CF₃), -111.6 (d of quartets,J_(q) =23 Hz, J_(d) =120 Hz) and -111.8 (d of quartets, J_(q) =23 Hz,J_(d) =120 Hz, vinyl F on C1 cis to CF₃), -123.6 (m, CF₂ CH₂), -134.3 to-135.3 (m, CFCH₂), -144.8 (m, central CF groups), -184.0 (overlapping m,vinyl F on C2 "Z"-ends), -190.2 (d of quartets, J_(d) =120 Hz, J_(q)=13.2 Hz) and -190.0 (d of quartest J_(q) =13 Hz, J_(q) =120 Hz, vinyl Fon C2 "E"-ends). Ratio of "E"-ends/"Z"-ends=35/65. ¹ H NMR (THF-d₈):4.81 (t, J=12.8 Hz, major), 4.88 (t, J=12.6 Hz, minor), 4.97 (d, J=11.2Hz, major), 5.04 (d, J=11.3 Hz, minor). E/Z ratio obtained from ¹⁹ F NMRdata. GC/MS (positive ion, EI) showed the major component with M⁺ ofm/z=870 and (M-F)=851, consistent with bis(vinyl) ether isomers of thetitle structure.

Example 3

Preparation of ##STR7##

A solution of (CH₃)₃ SiOCH(CH₃)CH₂ OSi(CH₃)₃ (4.32 g, 19.6 mmol) andtris (piperidino)sulfonium trimethyldifluorosilicate (TPSF) (100 mg),prepared as described in U.S. Pat. No. 4,940,402, in THF (20 mL) wastreated with perfluorocyclobutene (7.39 g, 45 mmol) while thetemperature was controlled between 30 and 35° C. The mixture was stirredat ambient temperature for 24 h. The reaction mixture was diluted withether, washed with ice water, dried (MgSO₄), and evaporated to give 4.58g of crude residue. Kugelrohr distillation (ca. 50° C. 0.1 mm) gave 3.72g of oil. ¹⁹ F NMR (CDCl₃ /F11) featured: -116.4 to -117.1 (m, 4 F),-118.9 to -119.7 (m, 4 F), -138.8 and -139.1 (equally intense m, 2 F).GC/MS showed one major component with M⁺ of m/z=360.0297. Calcd for C₁₁H₆ F₁₀ O₂ =360.0208. All these are consistent with the title compound.

Example 4

Preparation of ##STR8##

A solution of (CH₃)₃ SiO(CH₂)₃ OSi(CH₃)₃ (4.40 g, 20 mmol) and TPSF (100mg in 1.0 mL THF) in THF (20 mL) was treated with perfluorocyclobutene(4.4 mL, 45 mmol) while the temperature was controlled between 30 and35° C. The mixture was stirred at ambient temperature for 24 h. Thereaction mixture was diluted with ether, washed with ice water, dried(MgSO₄), and evaporated to give 6.68 g of light yello solid. GC analysis(method 1) showed one major component eluted at 10.3 min (92% purity).Kugelrohr distillation (ca. 50-55° C., 0.1 mm) gave 5.60 g of whilesolid, mp 43-45° C. ¹⁹ F NMR (CDCl₃ /F11): -116.8 (M, 4 F), -119.3 (m, 4F), -140.45 (m, 2 F). GC/MS showed one major component with M⁺ ofm/z=360.0225. Calcd for C₁₁ H₆ F₁₀ O₂ =360.0208. All these areconsistent with the title compound.

Example 5

Preparation of ##STR9##

A solution of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ (18.4 g, 78 mmol) andtris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF) (100 mg),prepared as described in U.S. Pat. No. 3,940,402, in THF (65 mL) wastreated with perfluorocyclobutene (18.5 mL, 180 mmol) while thetemperature was controlled between 25 and 30° C. Another 100 mg TASF wasadded, and the mixture was stirred at ambient temperature for 24 h. Thereaction mixture was diluted with ether, washed with ice water, dried(MgSO₄), and evaporated and Kugelrohr distilled to give 24.98 g ofcolorless oil. GC analysis (method 1) showed one major component(retention time=11.3 min), purity 94.5%. Spinning band distillation (70°C./0.05 mm) gave a sample with purity >98.6%. ¹⁹ F NMR (CDCl₃ /F11):-116.65 (m, 4 F), -119.5 (m, 4 F), -141.40 (m, 2 F). ¹ H NMR (CDCl₃):4.30 (m, 4 H), 1.92 (m, 4 H). GC/MS (positive ion, EI) showed onecomponent with highest observed mass of m/z=355.0463. Calcd for C₁₂ H₈F₉ O₂ =355.0380 (corresponding to M-F). Anal. Calcd for C₁₂ H₆ F₁₀ O₂ :C, 38.52; H, 2.16; F, 50.77. Found: C, 38.51; H, 2.31; F, 48.25. Allthese are consistent with the title compound.

Example 6

Preparation of ##STR10##

A solution of (CH₃)₃ SiO(CH₂)₅ OSi(CH₃)₃ (4.96 g, 20 mmol) and TPSF (100mg in 0.5 mL THF) in glyme (25 mL) at 0° C. was treated withperfluorocyclobutene (7.13 g, 44 mmol). The mixture was stirred atambient temperature for 24 h. The reaction mixture was diluted withether (200 mL), washed with ice water, saturated NaCl soln., dried(MgSO₄),and evaporated to give an oil which was fractionally kugelrohrdistilled. The major fraction, 4.77 g, bp 87° C. at 0.1 mm, consisted ofone major component (ca. 75%). ¹⁹ F NMR (CDCl₃ /F11): -116.5 (d, 4 F),-119.4 (m, 4 F), -141.5 (m, 2 F). GC/MS (positive ion, EI) showed onemajor component with M⁺ of m/z=388, corresponding to the desired 2/1adduct (title compound) (C₁₃ H₁₀ F₁₀ O₂).

Example 7

Preparation of ##STR11##

A solution of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃ (17.8 g, 49.9 mmol) inglyme (125 mL) at -50° C. was treated with perfluorocyclobutene (32.3 g,200 mmol) and cesium fluoride (0.5 g). The mixture was warmed to 0° C.and stirred for 2.5 h. It was then allowed to warm slowly to 25° C. over18 h. The mixture was diluted with ether, washed with water, dried,evaporated, and kugelrohr distilled to give 21.8 (88% yield) colorlessoil, bp 60° C. (0.1 mm). GC analysis (method 1) showed 99.6% purity. ¹⁹F NMR (THF-d₈): -117.15 (m, 4F), -119.8 (m, 4F), 120.7 (m, 4F), -125.3(s, 2F), -138.55 (m, 2F(vinyl)). ¹ H NMR (THF-d₈): 5.00 (m). All theseare consistent with the title compound.

Example 8

Preparation of ##STR12##

A solution of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃ CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃(17.0 g, 28.9 mmol) in glyme (75 mL) was treated withperfluorocyclobutene (20.7 g,128 mmol) at -40° C. CsF (0.5 g) was added,and the mixture was warmed slowly to 0° C. The mixture was stirred for2.5 h at 0° C., then for 18 h at 25° C. Excess perfluorocyclobutene andtrimethylsilylfluoride (TMSF) were removed under vacuum. The remainderwas diluted with ether, washed with water, dried and stripped to give21.9 g of crude product which was kugelrohr distilled to provide 19.2 g(82.4%) (bp 80-90° C./ca. 0.1 mm). IR: 1766 cm⁻¹ (C═C), 1373, 1241, and1138 cm⁻¹. ¹⁹ F NMR (THF-d₈): -79.77 and -80.85 (AB pattern, J_(AB) =150Hz, 2F), -80.0 (s, 3F), -82.5 (s, 3F), -83.2 (m, 2F), -117.3 (m, 4F),-120.0 (m, 4F), -123.7 (t, J=12.4 Hz, 2F), -135.6 (m, 1F), -138.0 (m,1F), -138.6 (m, 1F), -144.8 (apparent t, J=22 Hz, 1F). ¹ H NMR (THF-d₈):5.13 (d, J=12.4 Hz, 2H), 5.00 (t, J=12.6 Hz, 2H). GC/MS showed twocomponents, each with M⁺ of m/z=728. Also observed was M-F with m/z=709.

Example 9

Preparation of ##STR13##

A solution of (CH₃)₃ SiOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂ OSi(CH₃)₃(6.73 g, 8.93 mmol) in glyme (30 mL) was treated withperfluorocyclobutene (17.3 g, 107 mmol) at -55° C. TPSF (100 mg) wasadded, and the mixture was warmed slowly to 25° C. Excessperfluorocyclobutene and TMSF were removed under vacuum. The remainderwas stripped and kugelrohr distilled to give 7.39 g of colorless oil (bp80-85° C./0.05 mm, 92% purity, 85% yield). Spinning band distillationgave 5.91 g (bp 73-81° C., 0.05 mm). IR: 1766 cm⁻¹ (C═C). ¹⁹ F NMR(THF-d₈): -78.7 to -83.2 (m's, 15 F), -117.2 (m, 4F), -119.9 (m, 4F),-123.7 (t, J=12.5 Hz, 2F), -135.6 (m, 1F), -138.0 (m, 1F), -138.7 (m,1F), 145.0 (m, 2F). ¹ H NMR (CDCl₃): 4.75 (d, J=10.9 Hz, 2H), 4.62 (t,J=11.9 Hz, 2H). GC/MS showed a major component which exhibited a highmass fragment m/z=825, consistent with M--(CF₃). All these areconsistent with the title compound.

Example 10

Preparation of ##STR14##

A solution of (CH₃)₃ SiO(p-Ph)C(CF₃)₂ (p-Ph)OSi(CH₃)₃ (14.4 g, 30 mmol)in glyme (50 mL) at 0° C. was treated with TPSF (100 mg in 1.0 mLglyme).

Perfluorocyclobutene (11.3 g, 70 mmol) was added to the resultingsolution at 0-7° C. (ca. 10 min.). After addition was complete more TPSF(50 mg in 0.5 mL glyme) was added and the reaction mixture warmed to 25°C. After 3.0 h at this temperature, volatiles were removed under vacuum.The material was taken up in 1,1,2-trifluoro-1,2,2-trichloroethane(F113), washed with water, dried, and stripped to give 19.2 g ofresidue. Recrystallization from petroleum ether at -5° C. gave 12.7 g,mp 49-51° C. ¹⁹ F NMR (CDCl₃ F11): -64.46 (s, 6F), -117.5 (m, 4F),-118.9 (m, 4F), and -129.35 (m, 2F). ¹ H NMR (CDCl₃): 7.32 and 7.10(aryl AA'BB'). All these are consistent with the title compound.

Example 11

Preparation of CF₃ (F)C═C(CF₃)OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OC(CF₃)═C(F)CF₃

A solution of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃(2.86 g, 4.86 mmol) in glyme (25 mL) at -50° C. was treated withperfluoro-2-butene (3.2 g, 16 mol) and cesium fluoride (0.4 g). Themixture was warmed to 0° C. and stirred for 1.0 h. GC analysis(method 1) showed: one component at 5.9 min (12%), a group of sixresolved components at 7.9-8.3 min (49%), and a third group ofcomponents at 12.3-12.9 min (19%). The mixture was diluted with ether,filtered, and evaporated to give 4.3 g of crude residue. Fractionalkugelrohr distillation (0.1 mm) gave 0.6 g with bp ca. 25-30° C. The ¹⁹F NMR spectrum (THF-d₈) of this portion featured: -62.53 (q, J=11.4 Hz,--CF₃), -64.37 (q, J=11.4 Hz, --CF₃), -63.0 (m, --CF₃), -65.5 (m,--CF₃), -76.0 to -88.3 (m, --CF₃ +--OCF₂ --), -121.0 and -125.2 (ABpattern, J_(AB) =285 Hz, CF₂), -121.8 and -124.7 (AB pattern, J=285 Hz)-136.6 (m, CF), -139.6 (m, CF), -147.65 and -149.6 (m's, internal CFgroups). GC/MS exhibited M⁺ of m/z=604. These data are consistent onlywith diastereomeric 1/1 cyclic adducts. The next highest boilingfraction (1.5 g), collected at 55-100° C., consisted of cyclic 1/1adducts (18%) and isomeric bis(vinyl) ethers of the above structure. ¹⁹F NMR (THF-d₈) featured: -65.6 and -68.45 (m, --CF₃), -79.3 to 81.0 and-82.0 to -83.4 (m, CF₃ and OCF₂), -123.55 and -124.0 (m, CF₂ CH₂),-134.8 and -135.4 (m, CFCH₂), -138.0, -138.2, -142.6, and -143.8 (m's,vinyl F), -144.75 (m, central CF). ¹ H NMR 4.96 (d, J=10.5 Hz), 4.80 (t,J=12.5), 4.69 (d, J=11 Hz), 4.57 (t, J=12.4 Hz). IR: 1698 cm⁻¹ (C═C) andlarge absorption band 1285 to 1160 cm⁻¹. GC/MS showed a major group ofisomers, each with M⁺ of m/z=804, consistent with the assigned 2.1(title) adduct structures.

Example 12

Preparation of ##STR15##

A solution of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ (7.73 g, 33 mmol) and TPSF (50mg in 0.5 mL THF) in THF (20 mL) was treated with perfluorocyclopentene(14.8 g, 70 mmol) using a small stainless steel canula. Another 10 mgTPSF in 1.0 mL THF was added, and the mixture was stirred at ambienttemperature for 24 h. The reaction mixture was diluted with ether,washed with ice water, dried (MgSO₄), and evaporated to give 15.55 g, mp65-68° C. (>99%). Sublimation (45-50° C. at 0.1 mm) gave a sample withmp 67-70° C. GC analysis (method 1) showed one component (retentiontime=11.8 min). ¹⁹ F NMR (CDCl₃ /F11): -115.4 (d, J=12.7 Hz, 4F),-116.67 (d, J=10.6 Hz, 4F), -130.1 (s, 4F), -162.4 (M, 2F). Anal. Calcdfor C₁₄ F₁₄ H₈ O₂ : C, 35.46: H, 1.70; F, 56.09. Found: C, 34.48: H,1.75; F, 57.56. GC/MS (positive ion, EI) showed one component withhighest observed mass of m/z=265.0516. Calcd for C9H8F7O--265.0463. Thiscorresponds to M--(C₅ F₇ O). All these are consistent with the titlestructure.

Example 13

Preparation of (CF₃)₂ C═C(CF₂ CF₃)OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OC(CF₂ CF₃)═C(CF₃)₂

A mixture of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃(4.12 g, 7.0 mmol) perfluoro-2-methyl-2-pentene (12.6 g, 42 mmol), andglyme (20 mL) at 0° C. was treated with cesium fluoride (75 mg) andstirred for 1.5 h. The mixture was warmed to 25° C. and stirred for 4.0h. The mixture was distilled to provide 5.59 g of a colorless oil, bp75° C./0.05 mm. IR featured 1644 cm⁻¹ (C═C). ¹ H NMR (THF-d₈): 4.95 (d,J=13.7), 4.90 (t, J=12.4 Hz). ¹⁹ F NMR (THF-d₈) -56.3 (m, 6F), -59.1 (m,6F), -78.5 to -83.4 (m's, including CF₃ signals at -80.0, -80.9, -81.1,and -82.2, CF₂ O m at -83.2, and AB pattern, J_(AB) =140 Hz, at-79.2/-80.9, total of 16 F), -113.0 (m, 4F), -123.5 (s, 2F), -136.5 (m,1F), and -144.6 (m, 1F). GC analysis (method 1) showed two diastereomerswith retention time ca. 9.5 min. GC/MS showed the parent ion with M⁺ ofm/z=1003.918. Calcd for C₂₁ H₄ F₃₆ O₄ =1004.206. All these areconsistent with the title structure.

Example 14

Preparation of Macrocyclic Compounds

A solution of *C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (3.64 g,5.0 mmol) (*C₄ F₅ is perfluoro-1-cyclobutenyl) in glyme (175 mL) wastreated with cesium fluoride (100 mg). A sample of (CH₃)₃ SiOCH₂ (CF₂)₂OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃ (2.66 g, 4.52 mmol) was added over a1.0 h period. After 18 h at 25° C., the mixture was diluted with ether(50 mL), filtered, and evaporated to give 5.71 g of residue. Fractionalkugelrohr distillation gave 2.30 g, bp 110-130° C./0.05 mm. This portionwas refractionated to give 1.54 g, bp 110-120° C./0.05 mm. IR featured aband at 1752 cm⁻¹ (--C═C--), other bands at 1365, 1308, 1238, 1171,1112, 1071, and 1023 cm⁻¹. ¹⁹ F NMR (THF-d₈): -79.0 to -83.4 (m's, CF₃,OCF₂), -114.5 (m, a=48), -124.0 (m, CF₂ CH₂), -135.0 (m, CFCH₂), -144.7(m, central CF). ¹ H NMR: 4.93 (d, J=10.7 Hz), 4.79 (t, J=12.5 Hz). Massspectral analysis showed a large parent ion with nominal m/z=1132, asexpected for the cyclic dimers (C₂₆ H₈ F₃₆ O₈) of the formulas:##STR16##

A sample was further purified by preparative HPLC on Zorbax4/4 silica,eluting with 95/5 hexane/methyl t-butyl ether. Small amounts ofimpurities were thereby removed, and the central cut was homogeneous asjudged by GC analysis (method 1, retention time=13.94 min).

The pot residue was subjected to kugelrohr distillation and provided ahigher-boiling fraction (200-220° C.), 0.68 g. Mass spectral analysisshowed a substantial parent ion m/z=2264, consistent with a cyclictetramer of the repeat unit ##STR17##

To examine the role of catalyst in the cyclization process, the reactionwas repeated, using equimolar quantities of C₄ F₅ OCH₂ (CF₂)₂OCF(CF₃)CF₂ OCF(CF₃)CH₂)OC₄ F₅ and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂OCF(CF₃)CH₂)OSi(CH₃)₃ (5.0 mmol) in 100 mL glyme solution to which wasadded catalyst, either cesium fluoride (150 mg) or TASF (68 mg).Work-up, as above, gave: from the TASF reaction, 1.00 g 80% purity), andfrom the CsF reaction, 1.59 g (88% purity).

Example 15

Polymerization of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃with Hexafluoropropene

A weighed sample of hexafluoropropene (2.06 g, 13.7 mmol) was added toglyme (30 mL) at -50° C. (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ (8.08 g. 13.7 mmol) and cesium fluoride (15 mg) were added,and the mixture was warmed slowly to -10° C. After 0.5 h at -10° C., themixture was maintained at 0° C. for 2.0 h, then allowed to warm slowlyto 20° C. for 16 h. The supernatant was decanted, and solids were washedwith glyme to provide 2.99 g of rubbery solid and 4.10 f of solubleresidue after evaporation. IR (soluble fraction): 1732 cm⁻¹ (C═C).Lower-boiling components were removed by kugelrohr distillation (up to130° C. @0.05 mm) to give 3.0 g of residue. ¹⁹ F NMR (THF-d₈): -67.0 (m,a=25), -78.5 to -84.0 (m's, a=124), -124.0 (m, a=47), -135 (m, a=21),-145 (m, a=21), -178.7 to 181 (m's, a=7). Integration values for vinylCF and CF₃ and C═C signals were low. Size exclusion chromatographyshowed M_(n) =4900 for the major fraction of material. The data areconsistent with a polymer of the structure ##STR18##

Example 16

Polymerization of ##STR19##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (2.72 g,3.74 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃,(2.45 g, 4.16 mmol) in THF (20 mL) at reflux was treated with TASF (30mg in 1 mL THF). Heating of the mixture at reflux was continued for 15min. An aliquot was removed and analyzed by ¹⁹ F NMR and size exclusionchromatography. ¹⁹ F NMR (THF-d₈): -78.8 to -83.5 (m's, a=73), -114.8(s, a=18), -117.2 (m, a=3) and -119.8 (m, a=3), -123.8 and -124.2 (m's,combined a=12), -138.0 and -138.6 (m, a=1.5), -144.8 (m, a=12.5). Ratioof internal ring CF₂ signal to terminal ring CF₂ signal=3.0/1. Sizeexclusion chromatography showed the bulk of sample with M_(n) =3000,M_(w) =3800.

The data are consistent with a polymer of the structure ##STR20##

Example 17

Polymerization of ##STR21##

A solution of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (147 mg,0.25 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃,(182 mg, 0.25 mmol) in THF-d₈ (0.8 mL) was treated with TASd-10-camphorsulfinate (30 mg). ¹⁹ F NMR (THF-d₈): -78.5 to -83.5 (m's,a=73), -114.8 (s, a=22), -117.2 (m, a=2.7) and -119.8 (m, a=2.7), -124.0(m's, combined a=15), -135.5 (m, a=7), -144.8 (m, a=7) -157.2 (10 linemultiplet for Me₃ SiF, a=5). Ratio of internal ring CF₂ signal toterminal ring CF₂ signal=4.1/1.

The data are consistent with a polymer of the structure ##STR22##

Example 18

Polymerization of ##STR23##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (5.1049 g,7.01 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃,(4.123 g, 7.01 mmol) was treated with TASF (50 mg). The temperaturerapidly increased from 22 to 49° C., and TMSF was evolved rapidly. Afterthe exotherm subsided (ca. 1 h), the mixture was heated at 65° C. for1.25 h. After standing at room temperature for 48 h, another portion ofcatalyst (20 mg) was added and the mixture was heated at 70° C. for 1.0h. ¹⁹ F NMR (THF-d₈): -79.8 and 81.3 (AB pattern, J_(AB) =145 Hz (CF₂),a=21), -80.0 (s, a=31) and -82.5 (s, a=31, --CF₃ groups), -83.2 (brd s,a=21, CF₂), -114.9 (s, a-36, ring CF₂ groups), -117.2 (m, a=2) and-119.8 (m, a=2, terminal ring CF₂), -123.7 and -124.3 (s, combineda-21), -135.5 (m, a=9), -138.6 (m, a=1, terminal vinyl --F), -145.0 (m,a=10). Estimated M_(n) =13,700 from integrated intensities. ¹ H NMR:trace signals at 5.17 (d) and 5.02 (t), 4.95 (d) and 4.80 (t, combineda=51), 4.5 to 4.4 (brd m, a=2). Size exclusion chromatography showed thebulk of product with M_(n) =17,400, M₂ =24,900, in reasonable agreementwith NMR estimate. The data are consistent with a polymer of thestructure ##STR24##

A small amount of cyclic dimer C₂₆ H₈ F₃₆ O₈ (14%) was also produced.

Example 19

Polymerization of ##STR25##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (3.2650 g,4.484 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃,(2.639 g, 4.484 mmol) was treated with TPS benzoate (40 mg) prepared bythe addition of trimethylsilys benzoate to TPSF in THF following thegeneral procedure described in U.S. Pat. No. 4,588,795. The temperatureincreased gradually to 49° C., and TMSF was evolved. After the exothermsubsided, the mixture was heated at 25° C. for 4 h. ¹⁹ F NMR (THF-d₈):79.8 and -81.3 (AB pattern, J_(AB) =145 Hz (CF₂)), -80.0 (s) and -82.5(s), -83.2 (brd s), combined a=128, -114.9 (s, a-45), -117.2 (m, a=1)and -119.8 (m, a=1), -124.0 (m, a=25), -135.5 (m, a=12), -144.5 (m,a=12). ¹ H NMR: 4.90 (d) and 4.75 (t). Size exclusion chromatographyshowed the bulk of product with M_(n) =10,400. The data are consistentwith a polymer of the structure ##STR26##

Example 20

Polymerization of ##STR27##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (3.1468 g,4.32 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃,(2.543 g, 4.32 mmol) in trifluorotoluene (13 mL) was treated with TASF(30 mg, 0.11 mmol). The temperature increased to 30° C. After theexotherm subsided, the mixture was stirred for 0.75 h. A 0.8 mL aliquotwas removed, evaporated, and analyzed by ¹⁹ F NMR and size exclusionchromatography. ¹⁹ F NMR (THF-d₈): -79.0 to -83.5 (m's, a=78), -114.9(s, a=23), -117.2 (m, a=2.4) and -119.8 (m, a=2.4), -123.8 and -124.2(m's, combined a=14), -134.5 to -135.8 (m, a=7.5), -138.0 and -138.7 (m,a=1), -144.8 (m, a=7.3). Ratio of internal ring CF₂ signal to terminalring CF₂ signal=4.8/1. Size exclusion chromatography showed the bulk ofsample with M_(n) =7400, M_(w) =8500. The data are consistent with apolymer of the structure ##STR28##

A 0.11 g sample of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ was added, and the mixture was heated at 40° C. for 15 min andallowed to stand at 24° C. for 18 h. ¹⁹ F NMR analysis showed the ratioof internal ring CF₂ signal to terminal ring CF₂ signal=6.6/1. Sizeexclusion showed M_(n) =7700, M_(w) =9500.

Another 0.13 g of sample of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ was added, along with 15 mg TASF, and the mixture was heatedat 40° C. for 0.5 h. ¹⁹ F NMR showed the above mentioned ratio=11.8/1.Size exclusion chromatography showed M_(n) =9800, M_(w) =11,400. Thepresence of ca. 10%. cyclic dimer C₂₆ H₆ F₃₆ O₄ leads to a systematicoverestimate of M_(n) when using ¹⁹ F NMR integration.

Example 21

Polymerization of ##STR29##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃ CH₂ OC₄ F₅ (3.152 g,4.33 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃,(2.547 g, 4.33 mmol) in trifluorotoluene (15 mL) at 70° C. was treatedwith TPSF (30 mg, 0.076 mmol), The temperature increased rapidly to 77°C. After the exotherm subsided, the mixture was stirred for 0.5 h. A 0.8mL aliquot was removed, evaporated, and analyzed by ¹⁹ F NMR and sizeexclusion chromatography. ¹⁹ F NMR (THF-d₈): -79.0 and -83.5 (m's,a=116), -114.9 (s, a=34), -117.2 (m., a=4) and -119.8 (m, a=4), -123.8and 124.2 (m's, combined a=22), -134.5 to -136.0 (m, a=120), -138.0 and-138.7 (m, a=2), -144.8 (m, a=12). Ratio of internal ring CF₂ signal toterminal ring CF₂ signal=4.3/1. The data are consistent with a polymerof the structure ##STR30##

Size exclusion chromatography showed the bulk of sample with M_(n)=5700, M_(w) =6700.

A 0.25 g sample of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ and 30 mg catalyst were added, and the mixture was heated at80° C. for 1.0 h and at 90° C. for 2 h. ¹⁹ F NMR analysis showed theratio of internal ring CF₂ signal to terminal ring CF₂ signal=19/1. Sizeexclusion showed M_(n) =5100, M_(w) =7400,

Another 0.20 g sample of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ was added, along with 25 mg TPSF, and the mixture was heatedat 100° C. for 1.5 h. ¹⁹ F NMR analysis showed only trace signals forolefinic end groups. Size exclusion chromatography showed M_(n) =7700,M_(w) =11,100. The presence of ca. 10% cyclic dimer leads to asystematic overestimate of M_(n) when using the ¹⁹ F NMR integrationvalues.

Example 22

Polymerization of ##STR31##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃ CH₂ OC₄ F₅ (4.0895 g,5.616 mmol) in trifluorotoluene (15 mL) was treated with TPSF (30 mg,0.076 mmol) and heated rapidly to 50° C. (CH₃)₃ SiOCH₂ (CF₂)₂OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃, (3.367 g, 5.722 mmol) was added overa 5 min period by syringe, and the mixture was heated at 50° C. for 1.0h. A 0.8 mL aliquot was removed, evaporated, and analyzed by ¹⁹ F NMRand size exclusion chromatography. ¹⁹ F NMR (THF-d₈): -79.0 and -83.5(m's, a=137), -114.8 (s, a=46), -117.2 (m., a=2) and -119.8 (m, a=2),-124.2 (m, a=27), -135.0 (m, a=14), -145.0 (m, a=14). Ratio of internalring CF₂ signal to terminal ring CF₂ signal=11.5/1. Size exclusionchromatography showed the bulk of sample with M_(n) =7100, M_(w) =9800.The data are consistent with a polymer of the structure ##STR32##

A 0.2 g sample of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃and 20 mg catalyst was added, and the mixture was heated at 40° C. for2.0 h. ¹⁹ F NMR analysis showed the ratio of internal ring CF₂ signal toterminal ring CF₂ signal=30/1. Size exclusion showed M_(n) =10,200,M_(w) =13,000

Example 23

Polymerization of ##STR33##

A mixture of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃ CH₂ OC₄ F₅ (2.980 g,4.092 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃(2.408 g, 4.092 mmol) in THF (13 mL) was treated with TASF (27 mg, 2.5mol %). The temperature increased to 30° C. After the exotherm subsided,the mixture was stirred for 18 h at room temperature. An aliquot wasremoved and analyzed by ¹⁹ F NMR and size exclusion chromatography. ¹⁹ FNMR (THF-d₈): -79.0 to -83.5 (m's, a=130), -114.8 (s, a=35), -117.2 (m.,a=5.5) and -119.8 (m, a=5.5), -123.7 and -124.2 (m's, combined a=23),-135.5 (m, a=12.5), -138.0 and -138.6 (m, a=2.5), -144.8 (m, a=12.5).Ratio of internal ring CF₂ signal to terminal ring CF₂ signal=3.18/1.Size exclusion chromatography showed the bulk of sample with M_(n)=4200, M_(w) =5400. The data are consistent with a polymer of thestructure ##STR34##

A second addition of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ (0.28 g) and catalyst (2 mg) was made, followed by a 1.0 hperiod at 45° C. A third sample of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂OCF(CF₃)CH₂ OSi(CH₃)₃ was added, and the mixture was heated at 55° C.for 18 h. ¹⁹ F NMR analysis showed the ratio of internal ring CF₂ signalto terminal ring CF₂ signal=13.7/1. Size exclusion showed M_(n) =6900,M_(w) =9000.

Example 24

Polymerization of CF₃ CF═CFOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OCF═CFC₃with (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃

A solution of CF₃ CF═CFOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OCF═CFC₃(2.894 g, 4.11 mmol) in glyme (15 mL) at 20° C. was treated with cesiumfluoride (40 mg) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ (2.42 g, 4.11 mmol). The mixture was stirred for 18 h. Anadditional 0.24 g of (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃ was added, and the mixture was stirred for 18 h. The mixturewas diluted with glyme (50 mL), filtered, and evaporated to give 4.20 gof residue. ¹⁹ F NMR (THF-d₈): -66.9 and -67.8 (m, a=26), -78.5 to -83.8(m's, a=112), -123.7 and -123.9 (overlapping s, a=22), -135.0 (m, a=9),-145.0 (m, a=10), -178.2 to -181.0 (m's, a=7), -184.0 and -186.0 (m's,a=1). ¹ H NMR: 4.95 to 4.4 (m's), with trace signals at 4.4-4.2. Bothspectra are in accord with polymer consisting of 1,1-disubstitutedolefinic units. Size exclusion chromatography showed the major portionof the product with M_(n) =11,000. The data are consistent with apolymer of the structure ##STR35##

Example 25

Polymerization of CF₃ (F)C═C(CF)₃ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OC(CF₃)═C(F)CF₃ with (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃

A solution of CF₃ (F)C═C(CF)₃ OCH₂ (CF₂)₂ OCF(CF₃)CH₂ OC(CF₃)═C(F)CF₃(1.12 g. 1.39 mmol) in glyme (15 mL) was treated with cesium fluoride(30 mg) and (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃ (0.81g, 1.38 mmol). After 19 h at ambient temperature, ether was added, andthe mixture was filtered and evaporated to give 1.80 g of crude product.IR (thin film): 1698 (v. weak), 1667 cm⁻¹ (C═C). Low-boiling impurities(mainly the cyclic, 1/1 adduct from perfluoro-2-butene and (CH₃)₃ SiOCH₂(CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃, present in the sample of CF₃CF═CFOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OCF═CFC₃ ] were removed bykugelrohr distillation. ¹⁹ F NMR (THF-d₈) of residue after kugelrohrdistillation:: -63.5 to -65.8 (m's, combined a=84), -78.5 to -83.6 (m's,a=154), -123.5, -123.9, and -124.5 (m's, combined a=30), -135.8 (m,a=15), -144.9 (m, a=16). ¹ H NMR featured: 4.80 (t, J=11.4, a=10), 4.60(d, J=12.8) and 4.48 (t, J=12.0, combined a=42). Trace signals wereobserved at 4.95, 4.2, and 4.05. Size exclusion chromatography showedthe bulk of product with M_(n) =5500. The data are consistent with apolymer of the structure. ##STR36##

Also present was a component with M_(n) =1000, which suggests theformation of cyclic dimer, C₂₆ H₈ F₄₀ O₈, (mol wt=1208).

Example 26

Polymerization of (CF₃)₂ C═C(CF₂ CF₃)OCH₂ (CF₂)₂ OCF(CF₃ CF₂ OCF(CF₃)CH₂OC(CF₂ CF₃)═C(CF₃)₂ with (CH₃)₃ SiOCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OSi(CH₃)₃

A mixture of (CF₃)₂ C═C(CF₂ CF₃)OCH₂ (CF₂)₂ OCF(CF₃ CF₂ OCF(CF₃)CH₂OC(CF₂ CF₃)═C(CF₃)₂ (2.00 g. 2.0 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₂OCF(CF₃)CF₂ OCF(CF₃)CH₂ OSi(CH₃)₃ (1.18 g, 2.0 mmol) was treated withTPS benzoate (50 mg). The mixture was heated to 50° C., but TMSF was notproduced at a significant rate. The mixture was cooled to 25° C. andTASF (50 mg) was added. The viscous mixture was agitated occasionallyover a two hour period until TMSF evolution was complete. ¹⁹ F NMR(THF-d₈) of the soluble portion was complex, and the major difference,by comparison with NMRs of the starting components, was a significantdiminution of the signal intensity for the allylic CF₂ moieties. Theresidue was treated repeatedly with warm glyme to give a tacky, solidelastomer (1.23 g), and 1.19 g of residue after evaporation of solventfrom the soluble fraction. Size exclusion chromatography of the solublefraction showed starting material and low DP oligomers with M_(n) =1500to 3000. IR showed 1684 and 1646 cm⁻¹ (C═C). The data are consistentwith a polymer of the structure. ##STR37##

Example 27

Polymerization of (CF₃ (F)C═C(F)OCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂OC(F)═C(F)CF₃ with (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃

A solution of (CF₃ (F)C═C(F)OCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂OC(F)═C(F)CF₃ (1.74 g. 2.0 mmol) in glyme (20 mL) at -30° C. was treatedwith cesium fluoride (65 mg) and the (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃(0.71 g, 2.0 mmol). The mixture was warmed slowly to 0° C. and stirredfor 2.5 h. ¹⁹ F NMR analysis revealed complete conversion oftrimethylsilyl ether end groups to trimethylsilylfluoride. The mixturewas diluted with ether (30 mL), filtered, and evaporated to give 2.03 gof colorless, viscous oil. IR showed a trace absorption at 1768 cm⁻¹(characteristic of 1,1-dialkoxysubstituted HFP derivatives), and a largeenvelope with maximum absorptions at 1368, 1308, 1243, 1160, and 1080cm⁻¹. ¹⁹ F NMR (THF-d₈): -66.8 (m, a=3), -67.8 (m, 2=6), -78.2 to 84.0(m's, a=116), -120.5 (m, a=26), -123.7 (m, a=16), -125.0 (m, a=14),-134.5 (m, a=7), -145.0 (m, a=14), -180.5 and -181.0 (m's, a=8), -179.1and -184.0 (m's, a=2). ¹ H NMR : 5.0 to 4.6 (m's), with trace signals at5.1-5.0 and 4.4-4.2. Both spectra are in accord with polymer consistingof 1,1-disubstituted olefinic units. The data are consistent with apolymer of the structure ##STR38##

Size exclusion chromatography showed partially resolved bands with M_(n)ranging from 930 to 7800. The product was subjected to kugelrohrdistillation which provided 0.39 g of colorless, viscous oil. ¹ H NMR(THF-d₈): 4.59 (t, J=14 Hz) and 4.60 (t, J=14 Hz, combined a=60), 4.73(d, J=14.6) and 4.74 (d, J=14.5 Hz, combined a=55), 4.98 to 4.78 (m,a=90). GC/MS showed one major component with parent ion of m/z=1042,M--F=1023, and M--(CF₃)=973, consistent with the cyclic 1:1 adduct.

Example 28

Polymerization of ##STR39##

A solution of C₄ F₅ O(p-C₆ H₄)C(CF₃)₂ (p-C₆ H₄)OC₄ F₅ (3.10 g, 5.0 mmol)and P--(CH₃)₃ SiOCH₆ H₄ C(CF₃)₂ C₆ H₄ OSi(CH₃)₃ -p (2.40 g, 5.0 mmol) inglyme (20 mL) at 19° C. was treated with TPSF (50 mg). The exothermicreaction caused the temperature to increase to 26° C. The mixture washeated at 50° C. for 2.0 h, and then 75° C. for 0.5 h. The cooledmixture was filtered to provide 0.53 g of white solid, identified as thecyclic dimer (vide infra). Evaporation of solvent provided 4.42 g ofresidue. ¹⁹ F NMR (THF-d₈): -63.8 (s, a=137), -115.6 (s, a=70), -117.1(m, a=3.5), -119.0 (m, a=3.5), -130.4 (m, a=2), consistent with polymerof DP=21 (M_(n) =9600). IR (KBr wafer): 1760 cm⁻¹ (minor), 1728 (C═C),1610 and 1512 cm⁻¹. Size exclusion chromatography showed the major ofproduct with M_(n) =10,100 in good agreement with the NMR estimate. Thedata are consistent with a polymer of the structure: ##STR40##

The cyclic dimer was characterized as follows. High resolution massspectrum showed 916.35 (calcd for C₃₈ H₁₆ F₂₀ O₄ =916.07. A sample wassublimed at 210° C./0.04 mm to give mp=335-339° C. (sealed capillary).¹⁹ F NMR (THF-d₈): -63.70 (s, 12F), -115.85 (s, 8F). Anal. Calcd for C₃₈H₁₆ F₂₀ O₄ : C, 49.80; H, 1.76; F, 41.46. Found: C, 49.41; H, 1.83; F,41.66.

Example 29

Polymerization of ##STR41##

A solution of C₄ F₅ O(CH₂)₄ OC₄ F₅ (19 mmol) in propylene carbonate (15mL) was treated with cesium fluoride (200 mg) and (CH₃)₃ SiO(CH₂)₄OSi(CH₃)₃ (4.0 mL, 16 mmol). The mixture was heated to 85° C. for 1.5 h,cooled and treated with another portion (3 mmol) of (CH₃)₃ SiO(CH₂)₄OSi(CH₃)₃. After 16 h at 80 to 85° C., ¹⁹ F NMR analysis of the crudemixture showed: -113.2 (brd s, area=80), -145.9 (m, area=1), consistentwith perfluorocyclobutenyl-ended polymer. A sample was subjected to highvacuum to remove solvent. ¹ H NMR (CDCl₃) showed propylene carbonateresidues, OCH₂ and OCH₂ CH₂ resonances, and only a trace Me³ Si signal.Size exclusion chromatography showed a major component with M_(w) =2600,M_(n) =1750. The data are consistent with a polymer of the structure##STR42##

Example 30

Polymerization of ##STR43##

A solution of C₄ F₅ O(CH₂)₄ OC₄ F₅ (1.87 g, 5.00 mmol) and (CH₃)₃SiO(CH₂)₄ OSi(CH₃)₃ (1.11 g, 4.75 mmol) in glyme (15 mL) was treatedwith a solution of TPSF (48 mg in 0.5 mL glyme). The mixture was heatedslowly (ca. 0.5 h) to 65° C., then to 85° C. and stirred for 16 h. ¹⁹ FNMR (THF-d₈ /F11) of the crude mixture showed: -112.8 (m, area=111, CF₂groups of internal rings), -116.1 (m, area=9) and -119.5 (m, area=9, CF₂groups of terminal rings), -142.5 (m, area=4.5, vinyl F). Integrationindicated the average number of internal rings/chain=12.3 Size exclusionchromatography showed the major fraction of the polymer with M_(n)=5000, in reasonable agreement with ¹⁹ F NMR analysis. Removal ofsolvent under vacuum gave 2.30 g of viscous residue. The data areconsistent with a polymer of the structure ##STR44##

Example 31

Polymerization of ##STR45##

(A) Polymerization. A solution of C₄ F₅ O(CH₂)₄ OC₄ F₅ (3.74 g, 10.0mmol) and (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ (2.34 g, 10.0 mmol) in glyme (20mL) was treated with a solution of TPSF (100 mg in 1.0 mL glyme). Themixture was heated slowly to 85° C. and stirred for 18 h. ¹⁹ F NMRanalysis of the crude mixture showed (THF-d₈ /F11): -112.7 (m, area=81,CF₂ groups of internal rings), -115.9 (m, area=3) and -119.2 (m, area=3,CF₂ groups of terminal rings), -142.2 (m, area=1.5, vinyl F).Integration indicated the average number of internal rings/chain=27, orM_(n) =6100. Size exclusion chromatography showed the major fraction ofthe polymer with M_(w) =5170, M_(n) =5120, in good agreement with ¹⁹ FNMR analysis. The data are consistent with a polymer of the structure##STR46##

(B) Cyclic Dimer. Evaporation of solvent and treatment of the residuewith ether gave a small amount of crystalline solid. GC/MS analysisshowed one component with M⁺ of m/z=424.0887 (calcd for C₁₆ H₁₆ F₈ O₄=424.0920), consistent with a macrocyclic structure containing tworepeat units.

Example 32

Polymerization of ##STR47##

(A) Polymerization. A solution of C₄ F₅ OCH₂ (CF₂)O[CF(CF₃)CF₂ O]₂CF(CF₃)CH₂ OC₄ F₅ (1.83 g, 2.05 mmol) and (CH₃)₃ SiO(CF₂)₃ CH₂ OSi(CH₃)₃(0.729 g, 2.05 mmol) in glyme (20 mL) was treated with TPSF (35 mg inca.0.5 mL glyme), and an exothermic reaction took place. After 18 h atambient temperature, another 0.07 g of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂OSi(CH₃)₃ was added and the mixture was stirred for 20 h. A thirdaddition of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃ (0.07 g) was added andthe mixture was stirred for 18 h. A fourth addition of (CH₃)₃ SiOCH₂(CF₂)₃ CH₂ OSi(CH₃)₃ (0.04 g) was made and the reaction was stirred for48 h. Evaporation gave 2.30 g of very viscous resin. IR (thin film):1752 cm⁻¹ internal C═C). ¹ H NMR (THF-d₈): 4.98 (d, J=12 Hz, a=11), 4.85(m, a=29), 4.4 (minor m, a=6). ¹⁹ F NMR: -78.25 to -83.3 (m's, a=117),-114.7 (m, a=54), -117.2 (m, a=1), -119.8 (m, a=1), -121.0 (m, a=34),-124.0 (m, a=16), -125.0, -125.3, and -126.2 (singlets, combined a=20),-135.4 (m, a=7), -138.4 (m, a=1), -145.0 (m, a=15). Size exclusionchromatography showed a set of bands with M_(n) =6200. The data areconsistent with a polymer of the structure ##STR48##

(B) Cyclic Dimer. A significant fraction (ca. 25%) of material waseluted later and corresponded to M_(w) =1000. This product wasidentified as the macrocycle C₂₅ H₈ F₃₄ O₇ (n=1) by GC/MS which showed avery intense parent ion measured as 1067 (not accurately calibrated;theory=1066).

Example 33

Polymerization of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃ withPerfluorocyclobutene

A solution of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃ (8.0 g, 22.5 mm) inglyme (25 mL) at 5° C. was treated with TPSF (100 mg) in glyme (0.5 mL).Perfluorocyclobutene (8.1 g, 50 mmol) was added rapidly, while thetemperature was controlled between 0° C. to 15° C. with a dry-ice bath.After 3 h, most of the volatiles were removed under vacuum, and theresidue was partitioned with F113 (250 mL). The portion which did notdissolve readily was saved separately to give 3.85 g of foam afterevaporation of solvent. IR (thin film): 1752 cm⁻¹ (C═C). ¹⁹ F NMR(THF-d₈): -114.7 (S, a=13), -116 to -117 (m, a=10), -119 to -121.5 (m,a=52), -125 (m, a=25), -138.3 (m, a=1, vinyl F). Size exclusionchromatography showed the bulk of material with M_(n) =11,400. The dataare consistent with a polymer of the structure: ##STR49## and the cycliccompounds also have the same repeat unit, where n is 2, 3 or 4.

Product which readily dissolved in F113 was washed with water, dried,and evaporated to give 2.15 g of residue. Treatment of this residue withether and petroleum ether gave a small amouint of crystalline solid. ¹⁹F NMR (THF-d₈): -114.5 (s, ring CF₃), -120.6 (m, CH₂ CF₂), -125.1 (s,central CF₂). GC analysis (method 1): one component at 14.16 min (97%).GC/MS showed one component with intense M⁺ of m/z=668.0182 (C₁₈ H₈ F₂₀O₄), consistent only with the cyclic dimer. Crystals suitable for X-rayanalysis were grown by slow cooling of a saturated ether solution of thedimer. Mass spectral analysis of a kugelrohr distilled sample indicatedthe presence of cyclic trimer (1001.87, calcd=1002.02), and cyclictetramer (1335.8, calcd=1336.02).

Example 34

Polymerization of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃ withPerfluorocyclobutene

A solution of (CH₃)₃ SiOCH₂ (CF₂)₃ CH₂ OSi(CH₃)₃ (3.53 g, 10.0 mmol) inglyme (20 mL) at -20° C. was treated with TPSF (50 mg) in glyme (0.5mL). Perfluorocyclobutene (1.6 g, 10 mmol) was added rapidly, while thetemperature was controlled between -20 and 5° C. After 0.5 h at 15° C.,¹⁹ F NMR analysis of the mixture revealed complete conversion of Me₃Si-- groups to Me₃ SiF. Removal of volatiles provided 3.38 g ofcolorless, viscous residue. IR (thin film): 1752 cm⁻¹ (C═C), with minorshoulder at 1765 cm⁻¹. ¹⁹ F NMR (THF-d₈): -114.7 (s, a=13), -117.0 (m,a=11), -119.7 (m, a=9), -120.5 to -120.9 (m, a=105), -125.3 (s, a=52),-138.5 (m, a=4, vinyl F). Size exclusion chromatography showed the bulkof material with M_(n) =4300, along with ca. 10% cyclic dimer. The dataare consistent with the structure: ##STR50##

Example 35

Polymerization of (CH₃)₃ SiOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂OSi(CH₃)₃ with Perfluorocyclobutene

A solution of (CH₃)₃ SiOCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂ CF(CF₃)CH₂ OSi(CH₃)₃(5.00 g, 6.63 mmol) in glyme (20 mL) at 0° C. was treated with TPSF (50mg) in glyme (0.5 mL). Perfluorocyclobutene (2.5 g, 15 mmol) was addedrapidly, and the temperature was increased to -12° C. After 0.5 h at 20°C., ¹⁹ F NMR analysis of the mixture revealed complete conversion of Me₃Si groups to Me₃ SiF. Removal of volatiles provided 5.1 g of lightyellow, viscous residue. A 2.0 g sample was kugelrohr distilled to give0.67 g colorless oil, bp 85° C./0.07 mm, and 1.25 g of pot residue. IR(distilled sample): 1767 cm⁻¹ (C═C). ¹⁹ F NMR featured (THF-d₈): -78 to-84.5 (m, a=145), -117.3 (m, a=29), -120.0 (m, a=26), -123.7 (m, a=12),-135.5 (m, a=8), -138.0 and -138.7 (m's of equal area=13), -145.0 (m,a=15), consistent with the bis(vinyl) ether as the major component. ¹ HNMR features: 5.17 (d, J=12.3 Hz), and 5.03 (t, J=12.3 Hz). ¹⁹ F NMR ofthe pot residue: -79.0 to -83.4 (m's, a=121), -114.8 (s, a=13), -117.2(m, a=10), -120.0 (m, a=10), -123.6 (s) and -124.0 (s, a=13), -135.0 (m,a=7), -138.0 and -138.6 (m's, a=5), -145.0 (m, a=15), consistent withthe linear dimer end-capped by perfluorocyclobutene as the averagelength structure. Size exclusion chromatography showed unresolvedoligomers with M_(n) =4100 to 1200 (n=2 to 5). ¹ H NMR featured: 5.17(d, J=12.5) and 5.04 (t, J=12.5), 4.97 (d, J=12), and 4.80 (t, J=12).Comparison with the spectrum of the C₄ F₅ OCH₂ (CF₂)₂ O[CF(CF₃)CF₂ O]₂CF(CF₃)CH₂ OC₄ F₅ showed that the highest-field signals correspond toCH₂ groups close to internal rings (bearing two oxygen substituents).The data are consistent with a polymer of the structure: ##STR51##

Example 36

One-step Polymerization of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ withPerfluorocyclobutene

A solution of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ (4.60 g, 19.6 mmol) in THF (15mL) was treated with a solution of TPSF (50 mg) in THF (1 mL) bysyringe. Perfluorocyclobutene (3.09 g, 19 mmol) was added slowly over a40 min period, while the temperature was maintained at 25-29° C. Themixture was heated at 75° C. for 48 h. ¹⁹ F NMR (THF-d₈): -113. (m,area=81), -116.1 (m, area=33), -119.5 (m, area=32), -142.5 and -142.9(m's, area=16), consistent with an average DP=4.5, with vinyl endgroups. Further analysis was not carried out with this sample.Evaporation gave 2.24 g of yellow, viscous liquid. The data areconsistent with the structure: ##STR52##

Example 37

Polymerization of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ with Perfluorocyclopentene

A mixture of (CH₃)₃ SiO(CH₂)₄ OSi(CH₃)₃ (4.69 g, 20 mmol) and propylenecarbonate (20 mL) was treated with perfluorocyclopentene (4.2 g, 20mmol) and then with cesium fluoride (200 mg). The temperature rosesteadily from 21° to 42° C. After stirring at room temperature for 2 h,volatiles were removed under vacuum (0.05 mm) using temperatures up to95° C. There remained 5.5 g of viscous residue. ¹ H NMR of this portionshowed broad multiplets at 4.25 and 1.80, and contained no MeSi signals.¹⁹ F NMR exhibited: -111.2 to -112.5 (m's, area=112), -115.3 (m,area=43), -116.7 (m, area=42), -127.1 (m, area=15), -129.8 (m, area=60),-130.1 (s, area=42), -162.5 (m, area=21), consistent with oligomers ofaverage DP=4 containing perfluorocyclopentenyl end groups. Sizeexclusion chromatography showed one major component with M_(w) =1700,M_(n) =1200. IR (thin film) featured: 1750, 1725 and 1685 cm⁻¹. The dataare consistent with a polymer of the structure ##STR53##

Example 38

Fluorination of ##STR54##

A solution of C₄ F₅ OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅ (2.59 g,3.56 mmole) in F113 (370 mL) was placed in a translucent FEP reactorequipped with a stainless steel head. The reaction mixture was treatedwith elemental fluorine diluted with nitrogen (5% to 50% F₂) over a 2.3hr period: total # mmol F₂ used=53.4. After 33% of the fluorine had beenadded, an ultraviolet lamp (Sylvania #RSM 275 watt sunlamp) positionedoutside the reactor, was directed at the reactor and was turned on forthe remainder of the experiment. The resulting solution was purged withnitrogen, treated with sodium fluoride to remove HF, and filtered.Evaporation gave 3.40 g of colorless oil which was kugelrohr distilledto provide 1.76 g bp 43-60° C. (0.1 mm), and 0.39 g, bp 80-108° C. GCanalysis (method 1) showed ca. 92% purity and a yield of ca. 70%, ¹⁹ FNMR (F11): -80.0 to -83.8 (m, 14 F, CF₃ +OCF₂), -129.01 (s, 2F, CF₂),-131.15 and -134.19 (AB pattern, J_(AB) =230 Hz, 8F, ring CF₂ CF),-133.5 (unresolved m, 4F), -140.36 and -140.84 (m's, 1F each, ring CF),-145.2 (m, 2F, FC(CF₃)) COSY experiment showed major coupling patternswith ring CF_(a) F_(b) groups, CF₃ to CF, and OCF₂ to ring CF. GC/MSshowed the major component with highest observed mass ofm/e=694.9561770, corresponding to M--(C₄ F₇) (Calcd for C₁₃ F₂₅O4=694.939735. Also observed were 528.9586 (calcd for M--[C₄ F₇ +C₃ F₆O]=528.954402) and 362.9704900 (calcd for M--[C₄ F₇ +C₃ F₆ O+C₃ F₆]=362.969069). The data are consistent with a compound of the formula##STR55##

A 0.59 g sample of higher boiling material (127-133° C. @0.1 mm) wasobtained. GC/MS data (negative ion) were consistent with a dimericstructure of composition C₃₄ F₆₂ O₈ ; highest observed mass=1532.8231200(C₃₀ F₅₅ O₈ =1532.871485; assignment=M--(C₄ F₇); 1366.8830570 (C₂₇ F₄₉O₇ =1366.886152; assignment=M--[C₄ F₇ +C₃ F₆ O]).

Example 39

Fluorination of (CF₃)₂ C═C(CF₂ CF₃)OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OC(CF₂ CF₃)═C(CF₃)

A solution of CF₃ (CF₃)C═C(CF₂ CF₃)OCH₂ (CF₂)₂ OCF(CF₃)CF₂ OCF(CF₃)CH₂OC(CF₂ CF₃)═C(CF₃)₂ (5.00 g, 4.98 mmol) in F113 (370 mL) was placed in atranslucent Teflon® FEP reactor equipped with a stainless steel head andtreated with elemental fluorine diluted with nitrogen (5 to 50% F₂ overa 2.0 hr period; total # mmol F₂ used=59.8). After 28% of the fluorinehad been added, the ultraviolet lamp was turned on for the remainder ofthe experiment. The resulting solution was purged with nitrogen, treatedwith sodium fluoride to remove HF, and filtered. Evaporation gave 5.81 gof colorless oil which was kugelrohr distilled to provide 5.01 g bp70-75° C. (0.1 mm); bp (1 atmosphere) ca. 260° C. GC analysis (method 1)showed two groups of components (61% and 22% of total area). ¹⁹ F NMR(neat): -71.3 and -71.6 (m's, a=17) and -72.8 (s, a=16, terminal (CF₃)₂groups), -75.5 to -82.0 (brd m's) and -80.84, -80.96, -81.19 (singlets,combined a=64, OCF₂ +CF₃), -116.0 to -121.5 (m's, a=10, CF₂), -128.6 (s,a=6, internal CF₂), -133.2 and -133.6 (m's, combined a=5.3, CFO), -145.0(m, a=6.2, internal CF), -181.5 and -181.8 (m's, a=5.1, terminal CF).GC/MS (negative ion) showed the major component (no isomer separation onthis column) with highest observed mass of m/z=832.9291080,corresponding to M--(C₆ F₁₃) calcd for C₁₅ F₃₁ O4=832.930153. Alsoobserved were 666.9434200 (calcd for M--[C₄ F₁₃ +C₃ F₆ O]=666.9444820)and 500.9594120 (calcd for M--[C₆ F₁₃ +2C₃ F₆ O]=500.959487). The dataare consistent with a compound of the formula ##STR56##

Example 40

Fluorination of Polymer from Example 25

A solution of the polymer as prepared in Example 25 (0.89 g, 1.5 mequiv) in F113 (370 mL) was placed in a translucent Teflon® FEP reactorequipped with a stainless steel head and treated with elemental fluorinediluted with nitrogen (5 to 50% F₂ over a 2.0 hr period; total # mmol F₂used=18). After 33% of the fluorine had been added (1.0 hr), theultraviolet lamp was turned on for the remainder of the reaction. Theresulting solution was purged with nitrogen, treated with sodiumfluoride to remove HF, and filtered. Evaporation gave 1.13 g of viscousoil. IR (thin film) featured a large absorption envelope 1300-1100 cm⁻¹; C═C band of the starting vinyl polymer was absent. Anal. calcd for C₁₃F₂₆ O₄ : C, 21.87; F, 69:17; O, 8.96. Found: C, 22.37; F, 69.22; H,0.26. The data are consistent with the structure: ##STR57## with noolefinic groups or hydrogen remaining.

Example 41

Fluorination of Polymer from Example 16

A solution of the polymer as prepared in Example 16 (M_(n) =17,400)(6.49 g, 10.7 mequiv) in F113 (370 mL) was placed in a translucentTeflon® FEP reactor equipped with a stainless steel head and treatedwith elemental fluorine diluted with nitrogen (5 to 50% F₂ over a 3.0 hrperiod; total # mmol F₂ used=130). After 28% of the fluorine had beenadded (1.0 hr), the ultraviolet lamp was turned on for the remainder ofthe reaction. The resulting mixture was purged with nitrogen andfiltered to remove 2.18 g of white solid. The solution was treated withsodium fluoride and filtered. Evaporation gave 4.24 g of very viscousoil. ¹⁹ F NMR (neat, 100° C.): -78.0 to -85 (m, a=97), -123 to -134.5(m, a=38), -137.0 and -138.5 to -140.0 (m, a=8), -143.5 (m, a=12),-145.2 (m, a=12), in accord with the desired material based uponspectral analysis of the fluorination product from C₄ F₅ OCH₂ (CF₂)₂OCF(CF₃)CF₂ OCF(CF₃)CH₂ OC₄ F₅. Anal. Calcd for C₁₃ F₂₄ O₄ : C, 23.09;F, 67.44. Found: C, 22.98; F, 67.23. The solid material was submittedfor analysis also. Found: C, 23.40, 23.20; F, 67.12, 67.00. The data areconsistent with a polymer of the structure ##STR58## with no hydrogen orolefinic groups remaining.

Example 42

Fluorination of Cyclic Dimer from Example 14

A solution of the cyclic dimer as prepared in Example 14 (0.74 g, 0.65mmol) in F113 (370 mL) was placed in a translucent Teflon® FEP reactorequipped with a stainless steel head and treated with elemental fluorinediluted with nitrogen (5 to 50% F₂ over a 2.0 hr period; total # mmol F₂used=17.7). When 33% of the fluorine had been added (40 min), theultraviolet lamp was turned on for the remainder of the reaction. Theresulting mixture was purged with nitrogen, treated with sodiumfluoride, and filtered. Evaporation gave 0.95 g of colorless oil whichwas kugelrohr distilled to provide 0.59 g, bp 90-150° C. (0.1 mm). GC/MS(negative CI) showed the major component characterized by a parent ionof m/z=1351.889450 (calcd for C₂₆ F₄₈ O₈ =1351.882664), next-highestmass=1170.8878170 (calcd for C₂₂ F₄₁ O_(x) =1170.893843. M--(C₄ F₆ +F)next-highest mass=1004.9139250 (calcd for C₁₉ F₃₅ O₇ =1004.908510,M--[C₄ F₆ +C₃ F₆ O]). ¹⁹ F NMR (F11): -78.0 to -88.0 (m, a=60), -122.0(m, a=3.5), -125.0 to -133.0 (m, a=20), -138.0 to -140.0 (m, a=2.5),-145.0 (m, a=7). The data are consistent with a compound of the formula##STR59## B. Preparation of Macrocycle ##STR60##

A solution of ##STR61## (4.96 g., 10.0 mmol) and (CH₃)₃ SiOCH₂ (CF₂)₃CH₂ OSi(CH₃)₃ in glyme (500 mL) at -20° C. was treated with CsF (200mg). The mixture was warmed slowly to 25° C. and stirred for 18 hours.Another 120 mg of CsF and 0.6 g. of bis(silyl) ether were added and themixture was stirred for 24 hours. 200 mL of ether was added and themixture was filtered, evaporated and kugelrohr distilled to provide 3.48g. of white solid, bp 124-156° C. (0.1 mm). GC analysis showed two majorproducts in a 3.7/1 ratio. GC/MS showed both components with parent ionof m/z=668. Recrystallation from ether gave 2.88 g which contained ca.3% of the minor isomer. A second crystallization gave 2.27 g,mp=122-123° C. with purity >99.8%. ¹⁹ F NMR (THF-d₈): -114.53 (s, 8F),120.6 [m, 8F(CH₂ CF₂)], 125.06 (s, 4F); lineshapes were unchanged to-70° C. ¹ H NMR: 4.85 (m, pseudotriplet, temperature independent to -85°C.).

Example 43

Preparation of Macrocycle-Fluoride Adduct

A solution of macrocycle from Experiment 42B (446 mg, 0.67 mmol) in THF(3 mL) was added to a mixture of TAS trimethyldifluorosiliconate (184mg, 0.67 mmol) and THF (5 mL). The resulting colorless solution wasevaporated (ca. 1 mm) to give 571 mg of white solid, mp=108-110° C.(dec). Further purification and crystal growth was carried out asfollows. The solid was dissolved in 5 mL ether, and the soluble portionwas pipetted into a clean vial and cooled at -25° C. A small volume ofpetroleum ether was added slowly, and the mixture was cooled for anadditional 2 hrs. The mother-liquor was removed and the crystals weresubjected to vacuum to remove remaining solvent. The melting(decomposition) point was unchanged. ¹ H NMR (THF-d₈), 25° C.): 6.05(brd m, w_(1/2) =43 Hz, 8H), 2.96 (s, 18 H). ¹⁹ F NMR (THF-d₈, 25° C.):-76.0 (brd s, 1F), -117.10 (s, 8F), -123.67 (s, 8F), -131.1 (s, 4F).X-ray crystallographic analysis showed the complex anion to be of C₂symmetry, with the central fluoride held in place by four C--H--Finteractions.

Example 44

Group Transfer Polymerization of Methyl Methacrylate UsingMacrocycle-Fluoride Adduct from Example 43 as Catalyst.

A solution of (CH₃)₂ C═C(OCH₃)OSi(CH₃)₃ (0.62 g, 3.6 mmol) and methylmethacrylate (5.00 mL) in glyme (20 mL) was treated with a glyme (0.5mL) solution of the macrocyclic anion from Example 43 (15 mg, 0.018mmol). The temperature began to increase upon addition of the first fewdrops of catalyst, then rapidly increased to 56° C. After 1.0 hr at 25°C., a second portion of MMA (5.0 mL) was added. The temperatureincreased to 26° C. After 4.0 hrs. at 25° C., volatiles were removed togive 7.59 g of colorless, solid PMMA. GPC analysis revealed M_(w) =4820,M_(n) =2730, D=1.77.

Although the present invention has been described with reference to theparticular embodiments herein set forth, it is to be understood that thepresent disclosure has been made only by way of example and thatnumerous changes in the details of the processes and compositions hereinenumerated may be resorted to without departing from the spirit andscope of the invention should not be limited by the specification butonly by the scope of the claims appended hereto.

What is claimed is:
 1. A process for producing partially fluorinatedethers, comprising the catalyzed polycondensation of a silyl ether and afluorinated olefin in the presence of a suitable catalyst, conductedwithin a temperature range of -50° C. to 120° C.
 2. The process of claim1 wherein the catalyst is a source of fluoride ion.
 3. The process ofclaim 2 wherein the catalyst is selected from the group consisting ofCsF, tris(dialkylamino)sulfonium difluorotrimethylsilicate,tetrabutylammonium fluoride, tris(dialkylamino)sulfonium bifluoride,tris(piperidino)sulfonium bifluoride, tetraalkylammonium bifluorides andtetraarylphosphonium bifluorides.
 4. The process of claim 1 wherein thecatalyst is not a source of fluoride ion.
 5. The process of claim 4wherein the catalyst is selected from the group consisting of M⁺ ZCO₂ ⁻,M⁺ OC₆ H₄ NO₂ ⁻, and M⁺ ZSO₂, where z is a linear or branched alkylgroup containing from 1 to 10 carbon atoms or phenyl and M⁺ is anycation.
 6. The process of claim 5 wherein M⁺ is a cation of structure(Z'₂ N)₃ S⁺ where Z' is a linear or branched alkyl group containing from1 to 10 carbon atoms.
 7. The process of claim 2 conducted in thepresence of an inert solvent.
 8. The process of claim 4 conducted in thepresence of an inert solvent.
 9. The process of claims 7 or 8 conductedin a solvent selected from the group consisting of glyme andtetrahydrofuran.
 10. The process of claim 9 in which the molar range ofbis(silyl)ether to catalyst is from 4-10,000.
 11. The process of claim10 in which the molar range of perfluoroolefin to bis(silyl)ether isfrom 0.9 to 2.5.
 12. The process of claim 11 in which the concentrationof bis(silyl)ether in solution is greater than or equal to 0.1M.
 13. Theprocess of claim 1 wherein the bis(silyl)ether has the general formulaR² R³ R⁴ SiOROSiR⁵ R⁶ R⁷ and the fluorinated olefin has the formulaR_(f) ¹ (F)C═C(F)R_(f) ² wherein R², R³, R⁴, R⁵ R⁶, R⁷ are independentlyCH₃ -- or C₂ H₅ -- or one of R², R³, R⁴, R⁵ R⁶, and R⁷ may be C₆ H₅ --with the remainder of the groups being independently CH₃ -- or C₂ H₅ --;and R, R_(f) ¹ and R_(f) ² are as defined in claim
 1. 14. The process ofclaim 13 wherein R is --CH₂ (CF₂)₃ CH₂ --, and R², R³, R⁴, R⁵ R⁶, and R⁷are each --CH₃.
 15. A process for producing a polymer consistingessentially of the repeat unit --[R_(f) ¹ C═C(R_(f) ²)ORO]-- comprising,a condensation reaction of a bis(silyl)ether of the formula R² R³ R⁴SiOROSiR⁵ R⁶ R⁷ with a bis(vinyl) ether of the structure R_(f) ¹(F)C═C(R_(f) ²)OROC(R_(f) ²)═C(F)R_(f) ¹ in the presence of a suitablecatalyst,wherein: R is a diradical of the formula:--C_(x) H_(2x-y) F_(y)-- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2xfor a given value of x, but with the additional proviso that the carbonatoms containing the free valences of the diradical not be attached tofluorine atoms, and when x is an integer from 4 to 20 some of the carbonatoms may be internally interrupted with oxygen atoms forming etherstructures and with the proviso that the oxygen atoms be separated bytwo or more carbon atoms; --C₆ H_(4-a) F_(a) --, wherein a is 0, 1, 2,3, or 4; --C₁₀ H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to6 with the proviso that the radical bonds are not on adjacent carbonatoms; --C₁₂ H_(8-c) F_(c) --, wherein c is 0 or an integer of 1 to 8,with the proviso that the radical bonds are not on adjacent carbonatoms; or --CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer of 1 to 4, R¹ is --CH_(2-f) F_(f) --,wherein f is 0 or an integer from 1 to 2x; R_(f) ¹ and R_(f) ² areindependently --C_(z) F_(2z+1), wherein z is an integer from 1 to 10; orR_(f) ¹ and R_(f) ² taken together wherein R_(f) ¹ and R_(f) ² in thecis configuration are --(CF₂)_(m) --, wherein m is 2, 3 or 4, providedthat when R_(f) ¹ and R_(f) ² taken together are --(CF₂)_(m) --, R shallnot be --CH₂ (CF₂)_(s) CH₂ -- where s is an integer from 1 to 12 andwherein R², R³, R⁴, R⁵, R⁶, R⁷ are independently CH₃ -- or C₂ H₅ -- orone of R², R³, R⁴, R⁵, R⁶, and R⁷ may be C₆ H₅ -- with the remainder ofthe groups being independently CH₃ -- or C₂ H₅ --.
 16. The process ofclaim 15 wherein the molar ratio of bis(vinyl) ether to bis(silyl) etheris 0.9 to 1.5.
 17. The process of preparing a polymer consistingessentially of the repeat unit

    --[C(═CFR.sub.f.sup.1)OR.sup.8 O]--                    (B)

wherein R_(f) ¹ is --C_(z) F_(2z+1), wherein z is an integer from 1 to10 and wherein R⁸ is R, where R is a diradical of the formula --C_(x)H_(2x-y) F_(y) -- where x is an integer from 2 to 20, y is 0 or aninteger from 1 to 2x for a given value of x, but with the additionalproviso that the carbon atoms containing the free valence of thediradical not be attached to fluorine atoms, and when x is a integerfrom 4 to 20 some of the carbon atoms may be internally interrupted withoxygen atoms forming ether structures and with the proviso that theoxygen atoms be separated by two or more carbon atoms; --CH_(4-a) F_(a)--, wherein a is 0, 1, 2, 3, or 4; --C₁₀ H_(6-b) F_(b) --, wherein b is0 or an integer from 1 to 6, with the proviso that the radical bonds arenot on adjacent carbon atoms; --C₁₂ H_(8-c) F_(c) --, wherein c is 0 oran integer from 1 to 8, with the proviso that the radical bonds are noton adjacent carbon atoms; and --CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --,wherein d and e are independently 0 or an integer from 1 to 4, R¹ is--CH_(2-f) F_(f) --, wherein f is 0 or an integer from 1 to 2x; by apolycondensation reaction whereby a bis(silyl) ether of the formula, R²R³ R⁴ SiOROSiR⁵ R⁶ R⁷ and a perfluoroolefin of the formula R_(f) ¹(F)C═CF₂ are reacted in the presence of a catalyst, and wherein R², R³,R⁴, R⁵ R⁶, R⁷ are independently CH₃ -- or C₂ H₅ -- or one of R², R³, R⁴,R⁵ R⁶, and R⁷ may be C₆ H₅ -- with the remainder of the groups beingindependently CH₃ -- or C₂ H₅ --.
 18. The process of claim 17 whereinthe molar ratio of bis(silyl) ether to catalyst is from 4 to 10,000. 19.The process of claim 18 wherein the molar ratio of perfluoroolefin tobis(silyl) ether is from 0.9 to 2.5.
 20. The process of claim 19conducted in the presence of a solvent.
 21. The process of claim 20wherein the molar concentration of bis(silyl) ether in solution isgreater than or equal to 0.01M.
 22. The process of claim 21 conducted ata temperature of from -50° C. to 120° C.
 23. The process of claim 22wherein the solvent is selected from the group consisting of glyme andtetrahydrofuran.
 24. The process of preparing a macrocyclic compound ofthe structure:

    [C(R.sub.f.sup.1)═C(R.sub.f.sup.2)ORO].sub.w           (c)

wherein R is a diradical of the formula --C_(x) H_(2x-y) F_(y) -- wherex is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for agiven value of x, but with the additional proviso that the carbon atomscontaining the free valence of the diradical not be attached to fluorineatoms, and when x is a integer from 4 to 20 some of the carbon atoms maybe internally interrupted with oxygen atoms forming ether structures andwith the proviso that the oxygen atoms be separated by two or morecarbon atoms; --CH_(4-a) F_(a) --, wherein a is 0, 1, 2, 3, or 4; --C₁₀H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6, with theproviso that the radical bonds are not on adjacent carbon atoms; --C₁₂H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8, with theproviso that the radical bonds are not on adjacent carbon atoms; and--CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --CH_(2-f) R_(f) --,wherein f is 0 or an integer from 1 to 2x; and R_(f) ¹, R_(f) ², areindependently --C_(z) F_(2z+1), wherein z is an integer from 1 to 10; orR_(f) ¹ and R_(f) ² taken together where R_(f) ¹ and R_(f) ² in the cisconfiguration are --(CF₂)_(m) --, wherein m is 2, 3 or 4, provided thatwhen R_(f) ¹ and R_(f) ² are as defined, then R shall not be --CH₂(CF)_(s) CH₂ -- where s is an integer from 1 to 12, C₆ F₅ --, C₁₀ F₇ --or C₁₂ F₉ --, and w is 1, 2, 3 or 4; comprising a condensation reactionbetween a silyl ether of the formula R² R³ R⁴ SiOROSiR⁵ R⁶ R⁷ and aperfluoroolefin of the formula R_(f) ¹ (F)C═C(F)R_(f) ² in dilutesolution in a solvent in the presence of a catalyst, where R_(f) ¹ andR_(f) ² are as defined above and wherein R², R³, R⁴, R⁵ R⁶, R⁷ areindependently CH₃ -- or C₂ H₅ -- or one of R², R³, R⁴, R⁵ R⁶, and R⁷ maybe C₆ H₅ -- with the remainder of the groups being independently CH₃ --or C₂ H₅ --.
 25. The process of claim 24 where the solvent is selectedfrom the group consisting of glyme and tetrahydrofuran.
 26. The processof claim 24 wherein the catalyst is a source of fluoride ions.
 27. Theprocess of claim 25 where the catalyst is selected from the groupconsisting of CsF, tris(dialkylamino)sulfonium difluorotrimethylsilicate, tetrabutylammonium fluoride, tris(piperidino)sulfoniumdifluoride, tetraalkylammonium bifluorides and tetraarylphosphoniumbifluorides.
 28. The process of claim 27 wherein the molar ratio ofbis(silyl) ether to catalyst is from 4 to 10,000.
 29. The process ofclaim 28 wherein the molar ratio of perfluoroolefin to bis(silyl) etheris from 0.9 to 2.5.
 30. The process of claim 29 wherein theconcentration of bis(silyl)ether in solution is from 0.001M to 0.1M. 31.A process for preparing the macrocyclic compound of the structure:

    [C(R.sub.f.sup.1)═C(R.sub.f.sup.2)ORO].sub.w           (c)

wherein R_(f) ¹ and R_(f) ² are R_(f) ¹ and R_(f) ² are independently--C_(z) F_(2z+1), wherein z is an integer from 1 to 10; or R_(f) ¹ andR_(f) ² taken together where R_(f) ¹ and R_(f) ² in the cisconfiguration are --(CF₂)_(m) --, wherein m is 2, 3 or 4, provided thatwhen R_(f) ¹ and R_(f) ² are as defined, then R shall not be --CH₂(CF)_(s) CH₂ -- where s is an integer from 1 to 12, C₆ F₅ --, C₁₀ F₇ --or C₁₂ F₉ --, wherein w=2 or 4, comprising reacting a bis(vinyl)ether ofthe formula R_(f) ¹ (F)C═C(R_(f) ²)ORO(R_(f) ²)C═C(F)R_(f) ¹ with abis(silyl) ether of the formula R² R³ R⁴ SiOROSiR⁵ R⁶ R⁷ in dilutesolution in a solvent and in the presence of a catalyst, at atemperature of -50° C. to 120° C., wherein R¹ is --CH_(2-f) R_(f),wherein f is 0 or an integer from 1 to 2x; and wherein R_(f) ¹ and R_(f)² are independently --C_(z) F_(2z+1), wherein z is an integer from 1 to10; or R_(f) ¹ and R_(f) ² taken together where R_(f) ¹ and R_(f) ² inthe cis configuration are --(CF₂)_(m) --, wherein m is 2, 3 or 4,provided that when R_(f) ¹ and R_(f) ² are as defined, then R shall notbe --CH₂ (CF)_(s) CH₂ -- where s is an integer from 1 to 12, C₆ F₅ --,C₁₀ F₇ -- or C₁₂ F₉ --; and wherein R is a diradical of the formula--C_(x) H_(2x-y) F_(y) -- where x is an integer from 2 to 20, y is 0 oran integer from 1 to 2x for a given value of x, but with the additionalproviso that the carbon atoms containing the free valence of thediradical not be attached to fluorine atoms, and when x is a integerfrom 4 to 20 some of the carbon atoms may be internally interrupted withoxygen atoms forming ether structures and with the proviso that theoxygen atoms be separated by two or more carbon atoms; --CH_(4-a) F_(a)--, wherein a is 0, 1, 2, 3, or 4; --C₁₀ H_(6-b) F_(b) --, wherein b is0 or an integer from 1 to 6, with the proviso that the radical bonds arenot on adjacent carbon atoms; --C₁₂ H_(8-c) F_(c) --, wherein c is 0 oran integer from 1 to 8, with the proviso that the radical bonds are noton adjacent carbon atoms; and --CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --,wherein d and e are independently 0 or an integer from 1 to 4, R¹ is--CH_(2-f) R_(f) --, wherein f is 0 or an integer from 1 to 2x; andR_(f) ¹, R_(f) ², are independently --C_(z) F_(2z+1), wherein z is aninteger from 1 to 10; or R_(f) ¹ and R_(f) ² taken together where R_(f)¹ and R_(f) ² in the cis configuration are --(CF₂) _(m) --, wherein m is2, 3 or 4, provided that when R_(f) ¹ and R_(f) ² are as defined, then Rshall not be --CH₂ (CF)_(s) CH₂ -- where s is an integer from 1 to 12,C₆ F₅ --, C₁₀ F₇ -- or C₁₂ F₉ --, and w is 1, 2, 3 or
 4. 32. A processfor preparing A macrocyclic compound of the structure: ##STR62## whereinR_(f) ¹ is --C_(z) F_(2z+1), wherein z is an integer from 1 to 10, R⁸ isR and R is a diradical of the formula --C_(x) H_(2x-y) F_(y) -- where xis an integer from 2 to 20, y is 0 or an integer from 1 to 2x for agiven value of x, but with the additional proviso that the carbon atomscontaining the free valence of the diradical not be attached to fluorineatoms, and when x is a integer from 4 to 20 some of the carbon atoms maybe internally interrupted with oxygen atoms forming ether structures andwith the proviso that the oxygen atoms be separated by two or morecarbon atoms; --CH_(4-a) F_(a) --, wherein a is 0, 1, 2, 3, or 4;--C₁₀H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6, with theproviso that the radical bonds are not on adjacent carbon atoms; --C₁₂H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8, with theproviso that the radical bonds are not on adjacent carbon atoms; and--CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --CH_(2-f) F_(f) --,wherein f is 0 or an integer from 1 to 2x;and w is 1, 2, 3 or 4,comprising: reacting a bis(silyl)ether of the structure R² R³ R⁴SiOROSiR⁵ R⁶ R⁷ with a perfluoroolefin of the structure R_(f) ¹ (F)C═CF₂in dilute solution in solvent and in the presence of a catalyst at atemperature of -50° C. to 120° C., wherein R_(f) ¹ is --C_(z) F_(2z+1),wherein z is an integer from 1 to 10, and wherein R², R³, R⁴, R⁵ R⁶, R⁷are independently CH₃ -- or C₂ H₅ -- or one of R², R³, R⁴, R⁵ R⁶, and R⁷may be C₆ H₅ -- with the remainder of the groups being independently CH₃-- or C₂ H₅ --.
 33. The process of claim 32 wherein the catalyst is CsF,tris(dialkylamino)sulfonium difluorotrimethyl silicate,tetrabutylammonium fluoride, tris(piperidino)sulfonium difluoride,tetraalkylammonium bifluorides and tetraarylphosphonium bifluorides. 34.The process of claim 33 wherein the solvent is selected from the groupconsisting of glyme and tetrahydrofuran.
 35. A process for preparing abis(vinyl) ether of formula D of the structure:

    R.sub.f.sup.1 (F)C═C(R.sub.f.sup.2)OROC(R.sub.f.sup.2)═C(F)R.sub.f.sup.1 (D),

wherein: R is a diradical of the formula --C_(x) H_(2x-y) F_(y) -- wherex is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for agiven value of x, but with the additional proviso that the carbon atomscontaining the free valence of the diradical not be attached to fluorineatoms, and when x is a integer from 4 to 20 some of the carbon atoms maybe internally interrupted with oxygen atoms forming ether structures andwith the proviso that the oxygen atoms be separated by two or morecarbon atoms; --CH_(4-a) F_(a) --, wherein a is 0, 1, 2, 3, or 4; --C₁₀H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6, with theproviso that the radical bonds are not on adjacent carbon atoms; --C₁₂H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8, with theproviso that the radical bonds are not on adjacent carbon atoms; and--CH_(4-d) R_(d) --R¹ --CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --CH_(2-f) F_(f) --,wherein f is 0 or an integer from 1 to 2x; R_(f) ¹ and R_(f) ² areindependently --C_(z) F_(2z+1), wherein z is an integer from 1 to 10; orR_(f) ¹ and R_(f) ² taken together where R_(f) ¹ and R_(f) ² in the cisconfiguration are --(CF₂)_(m) --, wherein m is 2, 3 or 4, provided thatwhen R_(f) ¹ and R_(f) ² are as defined, then R shall not be --CH₂(CF)_(s) CH₂ -- where s is an integer from 1 to 12, C₆ F₅ --, C₁₀ F₇ --or C₁₂ F₉ --, comprising, reacting a bis(silyl) ether of the formula R²R³ R³ SiOROSiR⁵ R⁶ R⁷ and perfluoroolefin of the formula R_(f) ¹(F)C═C(F)R_(f) ² in the presence of a solvent and in the presence of acatalyst which is a source of fluoride ion, and wherein R², R³, R⁴, R⁵R⁶, R⁷ are independently CH₃ -- or C₂ H₅ -- or one of R², R³, R⁴, R⁵ R⁶,and R⁷ may be C₆ H₅ -- with the remainder of the groups beingindependently CH₃ -- or C₂ H₅ --.
 36. The process of claim 35 carried onin a solvent that does not react with the starting materials orsolvents.
 37. The process of claim 36 conducted within a temperaturerange of -50° C. to 120° C.
 38. The process of claim 37 wherein R², R³,R⁴, R⁵ R⁶, and R⁷ are methyl and R is --CH₂ (CF₂)₃ CH₂ --.
 39. Theprocess of claim 37 wherein R_(f) ¹ and R_(f) ² are each --CH₃.
 40. Aprocess for the preparation of

    composition R.sub.f.sup.1 (F)C═C(F)OR.sup.8 OC(F)═C(F)R.sub.f.sup.1 (E),

wherein: R_(f) ¹ is --C_(z) F_(2z+1), wherein z is an integer from 1 to10; R⁸ is R and is a diradical of the formula --C_(x) H_(2x-y) F_(y) --where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2xfor a given value of x, but with the additional proviso that the carbonatoms containing the free valence of the diradical not be attached tofluorine atoms, and when x is a integer from 4 to 20 some of the carbonatoms may be internally interrupted with oxygen atoms forming etherstructures and with the proviso that the oxygen atoms be separated bytwo or more carbon atoms; --CH_(4-a) F_(a) --, wherein a is 0, 1, 2, 3,or 4; --C₁₀ H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6,with the proviso that the radical bonds are not on adjacent carbonatoms; --C₁₂ H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8,with the proviso that the radical bonds are not on adjacent carbonatoms; and --CH_(4-d) F_(d) R¹ CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --CH_(2-f) F_(f) --,wherein f is 0 or an integer from 1 to 2x; comprising, a reaction of abis(silyl)ether of the structure R² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ with anexcess of perfluoroolefin of the structure R_(f) ¹ (F)C═CF₂, in asolvent and in the presence of a catalyst, wherein R², R³, R⁴, R⁵, R⁶,R⁷ are independently CH₃ -- or C₂ H₅ -- or one of R², R³, R⁴, R⁵ R⁶, andR⁷ may be C₆ H₅ -- with the remainder of the groups being independentlyCH₃ -- or C₂ H₅ --; and wherein R_(f) ¹ and R⁸ are as defined above. 41.A process for the preparation of

    R.sub.f.sup.1 R.sub.f.sup.2 C═C(R.sub.f.sup.6)OR.sup.8 OC(R.sub.f.sup.6)═CR.sub.f.sup.2 R.sub.f.sup.1        (E')

wherein: R_(f) ¹ and R_(f) ² are independently --C_(z) F_(2z+1), whereinz is an integer from 1 to 10; or R_(f) ¹ and R_(f) ² taken togetherwhere R_(f) ¹ and R_(f) ² are in the cis configuration are --(CF₂)_(m)--, wherein m is 2, 3 or 4, C₆ F₅ --, C₁₀ F₇ -- or C₁₂ F₉ ; and eachR_(f) ⁶ is independently the same as R_(f) ¹, comprising a reaction ofR² R³ R⁴ SiOR⁸ OSiR⁵ R⁶ R⁷ with an excess of perfluoroolefin of theformula structure R_(f) ¹ (F)C═CF₂, in a solvent and in the presence ofa catalyst, wherein R², R³, R⁴, R⁵ R⁶, R⁷ are independently CH₃ -- or C₂H₅ -- or one of R², R³, R⁴, R⁵ R⁶, and R⁷ may be C₆ H₅ -- with theremainder of the groups being independently CH₃ -- or C₂ H₅ -- and R⁸ isa diradical of the formula --C_(x) H_(2x-y) F_(y) -- where x is aninteger from 2 to 20, y is 0 or an integer from 1 to 2x for a givenvalue of x, but with the additional proviso that the carbon atomscontaining the free valence of the diradical not be attached to fluorineatoms, and when x is a integer from 4 to 20 some of the carbon atoms maybe internally interrupted with oxygen atoms forming ether structures andwith the proviso that the oxygen atoms be separated by two or morecarbon atoms; --CH_(4-a) F_(a) --, wherein a is 0, 1, 2, 3, or 4; --C₁₀H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6, with theproviso that the radical bonds are not on adjacent carbon atoms; --C₁₂H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8, with theproviso that the radical bonds are not on adjacent carbon atoms; and--CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --CH_(2-f) F_(f) --,wherein f is 0 or an integer from 1 to 2x.
 42. The process of claim 40or 41 wherein the catalyst is CsF.
 43. The process of claim 40 or 41wherein the molar ratio of perfluoroolefin to bis(silyl)ether is from2.2 to
 12. 44. The process of claim 40 wherein the solvent is selectedfrom the group consisting of glyme and tetrahydrofuran.
 45. A processfor preparing a polymer consisting essentially of the repeat unit:

    --[C(═CFR.sub.f.sup.1)OR.sup.8 O]--                    (B)

comprising, reacting a bis(silyl)ether of the structure R² R³ R⁴ SiOR⁸OSiR⁵ R⁶ R⁷ with a perfluoroolefin of the structure R_(f) ¹ (F)CF₂ or abis(vinyl) ether of the formula R_(f) ¹ (F)C═C(R_(f) ²)ORO(R_(f)²)C═C(F)R_(f) ¹ in the presence of a catalyst at a temperature of -50°C. to 120° C. wherein R_(f) ¹ and R_(f) ² are independently --C_(z)F_(2z+1), wherein z is an integer from 1 to 10, wherein R⁸ is R, and Ris a diradical of the formula --C_(x) H_(2x-y) F_(y) -- where x is aninteger from 2 to 20, y is 0 or an integer from 1 to 2x for a givenvalue of x, but with the additional proviso that the carbon atomscontaining the free valence of the diradical not be attached to fluorineatoms, and when x is a integer from 4 to 20 some of the carbon atoms maybe internally interrupted with oxygen atoms forming ether structures andwith the proviso that the oxygen atoms be separated by two or morecarbon atoms; --CH_(4-a) F_(a) --, wherein a is 0, 1, 2, 3, or 4; --C₁₀H_(6-b) F_(b) --, wherein b is 0 or an integer from 1 to 6, with theproviso that the radical bonds are not on adjacent carbon atoms; --C₁₂H_(8-c) F_(c) --, wherein c is 0 or an integer from 1 to 8, with theproviso that the radical bonds are not on adjacent carbon atoms; and--CH_(4-d) F_(d) --R¹ --CH_(4-e) F_(e) --, wherein d and e areindependently 0 or an integer from 1 to 4, R¹ is --CH_(2-f) F_(f) --,wherein f is 0 or an integer from 1 to 2x; wherein R⁸ is R and R², R³,R⁴, R⁵, R⁶, R⁷ are wherein R², R³, R⁴, R⁵ R⁶, R⁷ are independently CH₃-- or C₂ H₅ -- or one of R², R³, R⁴, R⁵ R⁶, and R⁷ may be C₆ H₅ -- withthe remainder of the groups being independently CH₃ -- or C₂ H₅ --. 46.The process of claim 45 wherein the temperature is -20° C. to +10° C.47. The process of claim 45 wherein the catalyst is cesium fluoride. 48.The process of claim 47 wherein the solvent is glyme or tetrahydrofuran.